WO2021172172A1

WO2021172172A1 - Method for producing active light sensitive or radiation sensitive resin composition, pattern forming method, and method for producing electronic device

Info

Publication number: WO2021172172A1
Application number: PCT/JP2021/006201
Authority: WO
Inventors: 文博吉野; 敬充冨賀; 佑真楜澤; 東　耕平; 田中　匠
Original assignee: 富士フイルム株式会社
Priority date: 2020-02-27
Filing date: 2021-02-18
Publication date: 2021-09-02
Also published as: JPWO2021172172A1; JP7310007B2; TW202138917A

Abstract

The present invention provides a method for producing an active light sensitive or radiation sensitive resin composition that is improved in terms of agglomeration defects caused by a starting material, a pattern forming method which uses this production method, and a method for producing an electronic device by means of: a method for producing an active light sensitive or radiation sensitive resin composition, said method sequentially comprising, in the following order, a step (1) wherein a resin, a compound that generates an acid upon irradiation with active light or radiation, an acid diffusion control agent and a solvent are put into a container, and a step (2) wherein at least one of the resin, the compound that generates an acid upon irradiation with active light or radiation, the acid diffusion control agent and the solvent is additionally put into the container that contains the resin, the compound that generates an acid upon irradiation with active light or radiation, the acid diffusion control agent and the solvent; a pattern forming method which uses this production method; and a method for producing an electronic device.

Description

A method for producing a sensitive light-sensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for producing an electronic device.

The present invention relates to a method for producing a sensitive light-sensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for producing an electronic device.

In the manufacturing process of semiconductor devices such as ICs (Integrated Circuits, integrated circuits) and LSIs (Large Scale Integrated Circuits, large-scale integrated circuits), microfabrication by lithography using sensitive light-sensitive or radiation-sensitive resin compositions is performed. It is done.
Examples of the lithography method include a method of forming a resist film with an actinic cheilitis or radiation-sensitive resin composition, exposing the obtained film, and then developing the film.

The sensitive light-sensitive or radiation-sensitive resin composition is a composition containing a resin, a compound that generates an acid by irradiation with active light or radiation (photoacid generator), an acid diffusion control agent, and a solvent. Is known (see, for example, Patent Document 1 and Patent Document 2).

Japanese Patent Application Laid-Open No. 2007-65488 Japanese Patent Application Laid-Open No. 2006-152255

However, according to the studies by the present inventors, a sensitive light-sensitive or radiation-sensitive resin composition (typically a resist composition) containing a resin, a photoacid generator, an acid diffusion control agent, and a solvent as materials. It was found that agglomeration defects due to the material occur in the product) depending on the manufacturing method. The "aggregation defect caused by the material" means a defect generated by the aggregation of the materials, and specifically, the actinic cheilitis or the actinic cheilitis formed from the radiation-sensitive resin composition. Alternatively, a pattern formed by exposing and developing a radiation-sensitive film (typically a resist film) can be evaluated using a defect evaluation device.

An object of the present invention is to form a pattern using a method for producing a sensitive light-sensitive or radiation-sensitive resin composition in which aggregation defects caused by materials are improved, and the above-mentioned method for producing a sensitive light-sensitive or radiation-sensitive resin composition. To provide a method and a method of manufacturing an electronic device.

The present inventors have found that the above problems can be solved by the following configuration.

<1>
The step (1) of putting a resin, a compound that generates an acid by irradiation with active light or radiation, an acid diffusion control agent, and a solvent into a container, and
The resin, the compound that generates an acid by irradiation with the active light or radiation, the acid diffusion control agent, and the compound that generates acid by irradiation with the active light or radiation in a container containing the solvent. A method for producing a sensitive light-sensitive or radiation-sensitive resin composition, which comprises the step (2) of adding at least one of the acid diffusion control agent and the solvent in this order.
<2>
The method for producing a sensitive actinic or radiation-sensitive resin composition according to <1>, wherein the step (2) is performed 30 minutes or more after the step (1) is completed.
<3>
Between the above steps (1) and the above steps (2)
The sensitivity according to <1> or <2>, which comprises the step (1-2) of mixing the resin, the compound that generates an acid by irradiation with the active light or radiation, the acid diffusion control agent, and the solvent. A method for producing a light-emitting or radiation-sensitive resin composition.
<4>
The method for producing a sensitive actinic or radiation-sensitive resin composition according to <3>, wherein the mixing time in the above step (1-2) is 2 hours or more.
<5>
The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to <3> or <4>, wherein the mixing time in the above step (1-2) is 4 hours or more.
<6>
The method for producing a sensitive actinic or radiation-sensitive resin composition according to any one of <3> to <5>, wherein the mixing time in the step (1-2) is 8 hours or more.
<7>
The actinic light-sensitive or radiation-sensitive resin composition according to any one of <1> to <6>, wherein the solid content concentration of the sensitive light-sensitive or radiation-sensitive resin composition is 10% by mass or more. Manufacturing method.
<8>
The compound that generates an acid by irradiation with active light or radiation is at least one selected from the compound represented by the following general formula (ZI-3) and the compound represented by the following general formula (ZI-4). , <1> to <7>, wherein the method for producing a sensitive light-sensitive or radiation-sensitive resin composition.

In the general formula (ZI-3),
R _1c to R _5c are independently hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group. , Nitro group, alkylthio group or arylthio group.
R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.
Any two or more of R _1c to R _5c _{, R 5c} and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y are each combined to form a ring structure. The ring structure may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Zc ^- represents an anion.

In the general formula (ZI-4),
l represents an integer of 0 to 2.
r represents an integer from 0 to 8.
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxycarbonyl group.
R ₁₄ represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a cycloalkylsulfonyl group. When _{a plurality of R 14s} exist, they may be the same or different.
Each of R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Bonded to two R ₁₅ each other may form a ring. When two R ₁₅ are combined to form a ring together, it may contain a hetero atom in the ring skeleton.
Z ^- represents an anion.
<9>
After the above step (1)
The sensitivity according to any one of <1> to <8>, wherein the contained substance in the container is divided into two or more fractions, and the physical properties are evaluated using at least one of the fractions. A method for producing a light-emitting or radiation-sensitive resin composition.
<10>
An organic film is formed using at least one of the above fractions, the film physical characteristics of the organic film are evaluated, and based on the result of the evaluation, the above step (2) is performed in order to adjust to the desired film physical properties. The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to <9>.
<11>
The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to <10>, wherein the film physical characteristics are at least one of sensitivity, film thickness, contact angle, complex refractive index, transmittance, and refractive index. ..
<12>
The sensitivity according to <9>, wherein the solution physical properties are evaluated using at least one of the above fractions, and the above step (2) is performed in order to adjust the solution physical characteristics to the desired solution physical properties based on the result of the evaluation. A method for producing a light-emitting or radiation-sensitive resin composition.
<13>
The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to <12>, wherein the solution physical characteristics are at least one of a complex refractive index, a transmittance, and a refractive index.
<14>
A step of forming a resist film on a substrate using a sensitive light-sensitive or radiation-sensitive resin composition produced by the production method according to any one of <1> to <13>.
The step of exposing the resist film to obtain the exposed resist film, and
The step of developing the exposed resist film using a developing solution to form a pattern, and
A pattern forming method.
<15>
A method for manufacturing an electronic device, including the pattern forming method according to <14>.

According to the present invention, a pattern formation using a method for producing a sensitive light-sensitive or radiation-sensitive resin composition in which aggregation defects caused by materials are improved, and the above-mentioned method for producing a sensitive light-sensitive or radiation-sensitive resin composition are used. Methods and methods of manufacturing electronic devices can be provided.

The schematic diagram of an example of the manufacturing apparatus which can be used in the manufacturing method of the actinic cheilitis or radiation-sensitive resin composition.

Hereinafter, an example of a mode for carrying out the present invention will be described.
The numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution includes a group having a substituent as well as a group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the "organic group" in the present specification means a group containing at least one carbon atom.

Further, in the present specification, the type of the substituent, the position of the substituent, and the number of the substituents when "may have a substituent" are not particularly limited. The number of substituents may be, for example, one, two, three, or more. Examples of the substituent include a monovalent non-metal atomic group excluding a hydrogen atom, and for example, the following substituent T can be selected.

(Substituent T)
Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy group such as methoxy group, ethoxy group and tert-butoxy group; aryloxy group such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and metoxalyl group and the like. Acrylic groups of: alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; Carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group, nitro group; formyl group ; And combinations of these.

The bonding direction of the divalent group described in the present specification is not limited unless otherwise specified. For example, in the compound represented by the general formula "LMN", when M is -OCO-C (CN) = CH-, the position bonded to the L side is * 1 and the N side. Assuming that the position bonded to * 2 is * 2, M may be * 1-OCO-C (CN) = CH- * 2, and * 1-CH = C (CN) -COO- * 2. There may be.

In the present specification, "(meth) acrylic" is a general term including acrylic and methacryl, and means "at least one of acrylic and methacrylic". Similarly, "(meth) acrylic acid" is a general term including acrylic acid and methacrylic acid, and means "at least one of acrylic acid and methacrylic acid".

In the present specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (also referred to as molecular weight distribution) (Mw / Mn) of the resin are GPC (Gel Permeation Chromatography) apparatus (HLC-manufactured by Toso). GPC measurement by 8120 GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Toso Co., Ltd., column temperature: 40 ° C., flow velocity: 1.0 mL / min, detector: differential refractometer It is defined as a polystyrene-equivalent value by a rate detector (Refractive Index Detector).

As used herein, the term "active light" or "radiation" refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, and electron beams (EB:). It means Electron Beam) and the like. As used herein, the term "light" means active light or radiation.
Unless otherwise specified, the term "exposure" as used herein refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, EUV, etc., but also electron beams and ions. Includes drawing with particle beams such as beams.

[Method for Producing Actinic Cheilitis or Radiation Sensitive Resin Composition]
The method for producing a sensitive light-sensitive or radiation-sensitive resin composition of the present invention is:
The step (1) of putting a resin, a compound that generates an acid by irradiation with active light or radiation, an acid diffusion control agent, and a solvent into a container, and
The resin, the compound that generates an acid by irradiation with the active light or radiation, the acid diffusion control agent, and the compound that generates acid by irradiation with the active light or radiation in a container containing the solvent. The step (2) of adding at least one of the acid diffusion control agent and the solvent is included in this order.

The present inventors have a sensitive light-sensitive or radiation-sensitive resin composition containing a resin, a compound that generates an acid by irradiation with active light or radiation (photoacid generator), an acid diffusion control agent, and a solvent. As a method for producing a product, first, a resin, a photoacid generator, an acid diffusion control agent, and a solvent are placed in a container, and then the resin, the photoacid generator, and the acid diffusion control are placed in a container containing these. It has been found that the aggregation defect caused by the material can be improved by adopting the method of adding at least one of the agent and the above solvent.
Although the mechanism by which the problem of the present invention is solved by the production method of the present invention is not always clear, the present inventors consider as follows.
When a resin, a photoacid generator, an acid diffusion control agent, and a solvent, which are materials of a sensitive light-sensitive or radiation-sensitive resin composition (typically a resist composition), are mixed, intermolecular force and ionic force and ionicity are mutual. Due to the action or the like, the materials are agglomerated with each other, and agglomeration defects caused by the materials are generated.
On the other hand, in the present invention, after the material is put into the container in the step (1), at least one of the materials is additionally added in the step (2) to form a sensitive light-sensitive or radiation-sensitive resin composition. To manufacture. According to the present invention, in the step (1), a certain amount of the material is put in a container in advance to form an agglomerate, and then the remaining material is added in the step (2) to form more than the previously formed material. It is considered that the formation of agglomerates can be prevented, and as a result, the agglomeration defects caused by the material can be improved.

Hereinafter, each process will be described in detail.

<Process (1)>
The step (1) is a step of putting a resin, a photoacid generator that generates an acid by irradiation with active light or radiation, an acid diffusion control agent, and a solvent into a container.
The container in the step (1) is not particularly limited, and for example, a known container used in the production of the actinic cheilitis or radiation-sensitive resin composition can be used. The container may or may not have a lid as long as it can contain each of the above components. The container may be hermetically sealed or hermetically sealed, and may not be hermetically sealed or may not be hermetically sealed. The material of the container is not particularly limited. The size of the container is not limited, and it may be a size suitable for ordinary laboratories or a size suitable for industrial production. The container may be capable of performing operations such as heating, pressurizing, and stirring the components contained therein. For example, a reaction vessel, a kettle (for example, a reaction kettle), a tank (for example, a stirring tank), or the like can be used as a container. The container has a mechanism for putting each component into the container (for example, introduction pipe), a mechanism for discharging from the container (for example, discharge pipe), and a mechanism for reintroducing what is discharged from the container into the container (circulation mechanism). ) Etc. may be provided.
The production method of the present invention can be carried out using an apparatus for producing a sensitive light-sensitive or radiation-sensitive resin composition, and the container of the step (1) is preferably a sensitive light-sensitive or radiation-sensitive resin composition. A stirring tank in a product manufacturing apparatus can be used.
The manufacturing apparatus that can be used in the present invention is not particularly limited, and a known manufacturing apparatus can be used.

FIG. 1 shows a schematic view of an example of a manufacturing apparatus that can be used in the method for manufacturing a sensitive light-sensitive or radiation-sensitive resin composition of the present invention.
In FIG. 1, the manufacturing apparatus 100 has a stirring tank 10, a stirring shaft 12 rotatably mounted in the stirring tank 10, a stirring blade 14 mounted on the stirring shaft 12, and a bottom and one end of the stirring tank 10. The circulation pipe 16 which is connected and the other end is connected to the upper part of the stirring tank 10, the filter 18 arranged in the middle of the circulation pipe 16, the discharge pipe 20 connected to the circulation pipe 16, and the end of the discharge pipe 20. It has a discharge nozzle 22 arranged in the portion.
It is preferable that the liquid contact portion (the portion in contact with the liquid) in the apparatus is lined or coated with a fluororesin or the like.

The stirring tank 10 is not particularly limited as long as it can contain a photoacid generator that generates an acid by irradiation with a resin, active light, or radiation, an acid diffusion control agent, a solvent, and the like, and a known stirring tank can be mentioned. Be done.
The shape of the bottom of the stirring tank 10 is not particularly limited, and examples thereof include a dish-shaped end plate shape, a semi-elliptical end plate shape, a flat end plate shape, and a conical end plate shape, and a dish-shaped end plate shape or a semi-elliptical end plate shape is preferable.
A baffle plate may be installed in the stirring tank 10 in order to improve the stirring efficiency.
The number of baffle plates is not particularly limited, and 2 to 8 plates are preferable.
The width of the baffle plate is not particularly limited, and is preferably 1/8 to 1/2 of the diameter of the stirring tank.
The length of the baffle plate in the height direction of the stirring tank is not particularly limited, but is preferably 1/2 or more, more preferably 2/3 or more of the height from the bottom of the stirring tank to the liquid level of the component to be charged. 3/4 or more is more preferable.

It is preferable that a drive source (for example, a motor or the like) (not shown) is attached to the stirring shaft 12. When the stirring shaft 12 is rotated by the drive source, the stirring blade 14 is rotated, and each component put into the stirring tank 10 is stirred.
The shape of the stirring blade 14 is not particularly limited, and examples thereof include a paddle blade, a propeller blade, and a turbine blade.

The stirring tank 10 may have a material charging port for charging various materials into the stirring tank.
The stirring tank 10 may have a gas introduction port for introducing gas into the stirring tank 10.
The stirring tank 10 may have a gas discharge port for discharging the gas inside the stirring tank 10 to the outside of the stirring tank.

The configuration of the apparatus for producing the sensitive light-sensitive or radiation-sensitive resin composition is not limited to FIG. 1, and at least a container (preferably a stirring tank) may be provided.
Further, in the stirring tank, a cleaning nozzle (for example, a spray ball) may be arranged in the upper part of the tank.

In the step (1), when each component is put into the container, the inside of the container may or may not be agitated.
The method of stirring is not particularly limited, but it is preferably performed by the stirring blade. The rotation speed of the stirring blade is not particularly limited, but is preferably 20 to 500 rpm (rotations per minute), more preferably 40 to 350 rpm, and even more preferably 50 to 300 rpm.

The method of putting each component in the container in the step (1) is not particularly limited.
For example, a method of charging various components from the material input port of the stirring tank can be mentioned. When adding various components, the components may be added sequentially or collectively. Further, when adding one kind of component, it may be added in a plurality of times.
Further, when each component is sequentially charged into the stirring tank, the order of charging is not particularly limited.
The time when the step (1) is completed (the end of the step (1)) is the resin to be put in the container in the step (1), the compound that generates an acid by irradiation with active light or radiation, and the acid diffusion control. This is when the agent and the solvent have been put into the container.

Hereinafter, the compounds that generate acid by irradiation with resin, active light or radiation, the acid diffusion control agent, and the solvent used in the step (1) will be described.

<Resin>
The resin is not particularly limited, and examples thereof include a resin having a group which is decomposed by the action of an acid to generate a polar group, an alkali-soluble resin, a surfactant, and a hydrophobic resin.
The resin used in the step (1) may be one kind or two or more kinds.

[Resin having a group that decomposes by the action of acid to produce a polar group]
A resin having a group which is decomposed by the action of an acid to generate a polar group (also referred to as “resin (A)”) will be described.

The resin (A) preferably has a repeating unit (Aa) having an acid-degradable group (hereinafter, also simply referred to as “repeating unit (Aa)”).
An acid-degradable group is a group that is decomposed by the action of an acid to produce a polar group. The acid-degradable group preferably has a structure in which the polar group is protected by a leaving group that is eliminated by the action of an acid. That is, it is preferable that the resin (A) has a repeating unit (Aa) having a group which is decomposed by the action of an acid to generate a polar group. The polarity of the resin having the repeating unit (Aa) is increased by the action of the acid, the solubility in the alkaline developer is increased, and the solubility in the organic solvent is decreased.

As the polar group, an alkali-soluble group is preferable, and for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonylamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkyl). Sulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and , An acidic group such as a tris (alkylsulfonyl) methylene group, and an alcoholic hydroxyl group.
Among them, as the polar group, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable.

Examples of the leaving group that are eliminated by the action of an acid include groups represented by the formulas (Y1) to (Y4).
Equation (Y1): -C (Rx ₁ ) (Rx ₂ ) (Rx ₃ )
Equation (Y2): -C (= O) OC (Rx ₁ ) (Rx ₂ ) (Rx ₃ )
Equation (Y3): -C (R ₃₆ ) (R ₃₇ ) (OR ₃₈ )
Formula (Y4): -C (Rn) (H) (Ar)

In the formula (Y1) and the formula (Y2), Rx ₁ to Rx ₃ independently represent an alkyl group (linear or branched chain) or a cycloalkyl group (monocyclic or polycyclic), respectively. When _{all of Rx 1} to Rx ₃ are alkyl groups (linear or branched chain), it is preferable that at least two of _{Rx 1} to Rx _{3 are methyl groups.}
Among them, Rx ₁ to Rx ₃ preferably independently represent a linear or branched alkyl group, and Rx ₁ to Rx ₃ may independently represent a linear alkyl group. More preferred.
Two of Rx ₁ to Rx ₃ may be combined to form a monocyclic ring or a polycyclic ring.
Examples _{of the alkyl group of Rx 1} to Rx ₃ include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. preferable.
Examples _{of the cycloalkyl groups of Rx 1} to Rx ₃ include a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The polycyclic cycloalkyl group of is preferred.
Examples of the _{cycloalkyl group formed by combining two of Rx 1} to Rx ₃ include a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, and a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca. A polycyclic cycloalkyl group such as an nyl group and an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
The _{cycloalkyl group formed by combining two of Rx 1} to Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.
The group represented by the formula (Y1) or the formula (Y2) is, for example, an embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-mentioned cycloalkyl group. Is preferable.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent substituent. R ₃₇ and R ₃₈ may be combined with each other to form a ring. Examples of the monovalent substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like. It is also preferable that R _{36 is a hydrogen atom.}

As the formula (Y3), a group represented by the following formula (Y3-1) is preferable.

Here, L ₁ and L ₂ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which these are combined (for example, a group in which an alkyl group and an aryl group are combined). ..
M represents a single bond or a divalent linking group.
Q is an alkyl group which may have a hetero atom, a cycloalkyl group which may have a hetero atom, an aryl group which may have a hetero atom, an amino group, an ammonium group, a mercapto group, or a cyano. Represents a group, an aldehyde group, or a group in which they are combined (for example, a group in which an alkyl group and a cycloalkyl group are combined).
As for the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be replaced with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.
It is preferable that _one of L 1 and L ₂ is a hydrogen atom and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
Q, M, and, at least two members to the ring (preferably, 5-membered or 6-membered ring) L ₁ may be formed.
From the viewpoint of pattern miniaturization, L ₂ is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of the secondary alkyl group include an isopropyl group, a cyclohexyl group and a norbornyl group, and examples of the tertiary alkyl group include a tert-butyl group and an adamantan ring group. In these aspects, Tg (glass transition temperature) and activation energy are high, so that in addition to ensuring the film strength, fog can be suppressed.

In the formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may be combined with each other to form a non-aromatic ring. Ar is more preferably an aryl group.

As the repeating unit (Aa), the repeating unit represented by the formula (Aa1) is also preferable.

L ₁ represents a divalent linking group which may have a fluorine atom or an iodine atom, and R ₁ is an alkyl group which may have a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom or an iodine atom. Or, it represents an aryl group which may have a fluorine atom or an iodine atom, and R ₂ represents a desorbing group which is eliminated by the action of an acid and may have a fluorine atom or an iodine atom. However, _{at least one of L 1} , R ₁ , and R ₂ has a fluorine atom or an iodine atom.
L ₁ represents a divalent linking group which may have a fluorine atom or an iodine atom. The fluorine atom or a linking group may divalent have a iodine atom, -CO -, - O -, - S -, - SO -, - SO 2 -, have a fluorine atom or an iodine atom Examples thereof include a hydrocarbon group which may be used (for example, an alkylene group, a cycloalkylene group, an alkaneylene group, an arylene group, etc.), a linking group in which a plurality of these groups are linked, and the like. Among them, in terms of the effect of the present invention is more excellent, as the L _1, -CO-, or, - arylene - alkylene group having a fluorine atom or iodine atom - are preferred.
As the arylene group, a phenylene group is preferable.
The alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable.
The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but 2 or more is preferable, 2 to 10 is more preferable, and 3 to 10 is more preferable in that the effect of the present invention is more excellent. 6 is more preferable.

R ₁ represents an alkyl group which may have a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom.
The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable.
The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, but 1 or more is preferable, 1 to 5 is more preferable, and 1 to 1 to 5 is preferable in that the effect of the present invention is more excellent. 3 is more preferable.
The alkyl group may have a hetero atom such as an oxygen atom other than the halogen atom.

R ₂ represents a leaving group that is eliminated by the action of an acid and may have a fluorine atom or an iodine atom.
Among them, examples of the leaving group include groups represented by the formulas (Z1) to (Z4).
Equation (Z1): -C (Rx ₁₁ ) (Rx ₁₂ ) (Rx ₁₃ )
Equation (Z2): -C (= O) OC (Rx ₁₁ ) (Rx ₁₂ ) (Rx ₁₃ )
Equation (Z3): -C (R ₁₃₆ ) (R ₁₃₇ ) (OR ₁₃₈ )
Equation (Z4): -C (Rn ₁ ) (H) (Ar ₁ )

In the formulas (Z1) and (Z2), Rx ₁₁ to Rx ₁₃ are alkyl groups (linear or branched) or fluorine atoms which may independently have a fluorine atom or an iodine atom, respectively. Represents a cycloalkyl group (monocyclic or polycyclic) that may have an iodine atom. When _{all of Rx 11} to Rx ₁₃ are alkyl groups (linear or branched chain), it is preferable that at least two of _{Rx 11} to Rx _{13 are methyl groups.}
Rx ₁₁ to Rx ₁₃ _{are the same as Rx 1} to Rx _{3 in} (Y1) and (Y2) described above, except that they may have a fluorine atom or an iodine atom, and are an alkyl group and a cycloalkyl group. It is the same as the definition and the preferable range of.

In formula (Z3), R ₁₃₆ to R ₁₃₈ each independently represent a hydrogen atom, or a monovalent substituent that may have a fluorine atom or an iodine atom. R ₁₃₇ and R ₁₃₈ may be combined with each other to form a ring. The monovalent substituent which may have a fluorine atom or an iodine atom includes an alkyl group which may have a fluorine atom or an iodine atom, and a cycloalkyl group which may have a fluorine atom or an iodine atom. , An aryl group that may have a fluorine atom or an iodine atom, an aralkyl group that may have a fluorine atom or an iodine atom, and a group that combines these (for example, a combination of an alkyl group and a cycloalkyl group). Atom).
The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a hetero atom such as an oxygen atom in addition to the fluorine atom and the iodine atom. That is, in the above-mentioned alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, even if one of the methylene groups is replaced with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group. good.

As the formula (Z3), a group represented by the following formula (Z3-1) is preferable.

Here, L ₁₁ and L ₁₂ independently have an alkyl group selected from the group consisting of a hydrogen atom; a fluorine atom, an iodine atom and an oxygen atom; a fluorine atom, an iodine atom and an alkyl group. A cycloalkyl group which may have a hetero atom selected from the group consisting of oxygen atoms; an aryl group which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; or , A group in which these are combined (for example, a group in which an alkyl group and a cycloalkyl group are combined, which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom).
M ₁ represents a single bond or a divalent linking group.
Q ₁ represents a fluorine atom, an alkyl group which may have a hetero atom selected from the group consisting of iodine atoms and an oxygen atom; Yes fluorine atom, a hetero atom selected from the group consisting of iodine atoms and an oxygen atom May have a cycloalkyl group; may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; an amino group; an ammonium group; a mercapto group; a cyano group; an aldehyde group. ; Or, it represents a group in which these are combined (for example, a group in which an alkyl group and a cycloalkyl group are combined, which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom). ..

In formula (Y4), Ar ₁ represents an aromatic ring group which may have a fluorine atom or an iodine atom. Rn ₁ may have an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, or an aryl which may have a fluorine atom or an iodine atom. Represents a group. Rn ₁ and Ar ₁ may be combined with each other to form a non-aromatic ring.

As the repeating unit (Aa), a repeating unit represented by the general formula (AI) is also preferable.

In the general formula (AI)
Xa ₁ represents a hydrogen atom or an alkyl group which may have a substituent.
T represents a single bond or a divalent linking group.
Rx ₁ to Rx ₃ independently represent an alkyl group (linear or branched chain) or a cycloalkyl group (monocyclic or polycyclic). However, when _{all of Rx 1} to Rx ₃ are alkyl groups (linear or branched chain), it is preferable that at least two of _{Rx 1} to Rx _{3 are methyl groups.}
Two of Rx ₁ to Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

Represented by xa _1, as the alkyl group which may have a substituent group, include groups represented by methyl group or _-CH 2 _{-R 11.} R ₁₁ represents a halogen atom (fluorine atom or the like), a hydroxyl group or a monovalent substituent. For example, the halogen atom may be substituted, an alkyl group having 5 or less carbon atoms, or a halogen atom may be substituted. Examples thereof include an acyl group having 5 or less carbon atoms and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferable, and a methyl group is more preferable. As Xa ₁ , a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferable.

Examples of the divalent linking group of T include an alkylene group, an aromatic ring group, an -COO-Rt- group, an -O-Rt- group and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and is preferably a -CH _2- group,- (CH ₂ ) _2- group, or- (CH ₂ ) _3- Groups are more preferred.

Examples _{of the alkyl group of Rx 1} to Rx ₃ include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. preferable.
Examples _{of the cycloalkyl group of Rx 1} to Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The polycyclic cycloalkyl group of is preferred.
As the _{cycloalkyl group formed by combining two of Rx 1} to Rx ₃ , a cyclopentyl group and a monocyclic cycloalkyl group such as a cyclohexyl group are preferable, and in addition, a norbornyl group and a tetracyclodecanyl group are used. , Tetracyclododecanyl group, and polycyclic cycloalkyl group such as adamantyl group are preferable. Of these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable.
The _{cycloalkyl group formed by combining two of Rx 1} to Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.
As the repeating unit represented by the general formula (AI), for example, it is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-mentioned cycloalkyl group.

When each of the above groups has a substituent, the substituents include, for example, an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms) and the like. The number of carbon atoms in the substituent is preferably 8 or less.

The repeating unit represented by the general formula (AI) is preferably an acid-degradable (meth) acrylic acid tertiary alkyl ester-based repeating unit (Xa ₁ represents a hydrogen atom or a methyl group, and T is a single bond. It is a repeating unit that represents.

The resin (A) may have one type of repeating unit (Aa) alone, or may have two or more types.
The content of the repeating unit (Aa) (total content when two or more repeating units (Aa) are present) is 15 to 80 mol% with respect to all the repeating units in the resin (A). Is preferable, and 20 to 70 mol% is more preferable.

The resin (A) has at least one repeating unit selected as the repeating unit (Aa) from the group consisting of the repeating units represented by the following general formulas (A-VIII) to (A-XII). Is preferable.

In the general formula (A-VIII), R ₅ represents a tert-butyl group, a 1,1'-dimethylpropyl group, or a -CO-O- (tert-butyl) group.
In the general formula (A-IX), R ₆ and R ₇ each independently represent a monovalent substituent. Examples of the monovalent substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like.
In the general formula (AX), p represents 1 or 2.
In the general formulas (AX) to (A-XII), R ₈ represents a hydrogen atom or an alkyl group _{having 1 to 3 carbon atoms, and R 9} represents an alkyl group having 1 to 3 carbon atoms.
In the general formula (A-XII), R ₁₀ represents an alkyl group having 1 to 3 carbon atoms or an adamantyl group.

The resin (A) has a repeating unit having a polar group such as an acid group, a lactone structure, a sultone structure, a carbonate structure, and a hydroxyadamantan structure, in addition to the repeating unit (Aa) having an acid-degradable group. May be good.

(Repeating unit with acid group)
The resin (A) may have a repeating unit having an acid group.
As the repeating unit having an acid group, a repeating unit represented by the following general formula (B) is preferable.

R ₃ represents a hydrogen atom or a monovalent substituent which may have a fluorine atom or an iodine atom. The fluorine atom or an iodine atom monovalent substituent which may have a group represented by -L ₄ -R ₈ are preferred. L ₄ represents a single bond or an ester group. R ₈ is an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, and the like. Alternatively, a group combining these can be mentioned.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.

L ₂ represents a single bond or an ester group.
L ₃ represents a (n + m + 1) -valent aromatic hydrocarbon ring group or a (n + m + 1) -valent alicyclic hydrocarbon ring group. Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group. The alicyclic hydrocarbon ring group may be monocyclic or polycyclic, and examples thereof include cycloalkyl ring groups.
R ₆ represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). When R ₆ is a hydroxyl group, L ₃ is preferably an aromatic hydrocarbon ring group having a (n + m + 1) valence.
R ₇ represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
m represents an integer of 1 or more. m is preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.
n represents an integer of 0 or 1 or more. n is preferably an integer of 1 to 4.
In addition, (n + m + 1) is preferably an integer of 1 to 5.

As the repeating unit having an acid group, a repeating unit represented by the following general formula (I) is also preferable.

In general formula (I),
R ₄₁ , R ₄₂ and R ₄₃ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may _{be bonded to Ar 4} to form a ring, in which case R ₄₂ represents a single bond or an alkylene group.
X ₄ represents a single bond, -COO-, or -CONR _64- , and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond or an alkylene group.
Ar ₄ represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when combined with _{R 42 to form a ring.}
n represents an integer from 1 to 5.

_{The alkyl groups of R 41} , R ₄₂ , and R ₄₃ in the general formula (I) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, and 2-ethylhexyl. Alkyl groups having 20 or less carbon atoms such as groups, octyl groups, and dodecyl groups are preferable, alkyl groups having 8 or less carbon atoms are more preferable, and alkyl groups having 3 or less carbon atoms are further preferable.

_{The cycloalkyl groups of R 41} , R ₄₂ , and R ₄₃ in the general formula (I) may be monocyclic or polycyclic. Of these, a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group is preferable.
_{Examples of the halogen atoms of R 41} , R ₄₂ , and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
The alkyl group contained in the alkoxycarbonyl group _{of R 41} , R ₄₂ , and R ₄₃ in the general formula (I) is preferably the same as the alkyl group in _{R 41} , R ₄₂ , and R _43.

Ar ₄ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group when n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylen group, a naphthylene group, and an anthracenylene group. , Or an aromatic containing a heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrol ring, a triazine ring, an imidazole ring, a benzoimidazole ring, a triazole ring, a thiazazole ring, and a thiazole ring. Ring groups are preferred.

As a specific example of the (n + 1) -valent aromatic ring group when n is an integer of 2 or more, (n-1) arbitrary hydrogen atoms are removed from the above-mentioned specific example of the divalent aromatic ring group. There is a group that is made up of. The (n + 1) -valent aromatic ring group may further have a substituent.

Examples of the substituents that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1) -valent aromatic ring group can have include R ₄₁ , R ₄₂ , and R 41 in the general formula (I). , R ₄₃ , an alkoxy group such as an alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; an aryl group such as a phenyl group; and the like.
_-CONR 64 represented by X ₄ - _{(R 64} represents a hydrogen atom or an alkyl group) The alkyl group for _{R 64} in, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, sec- Examples thereof include alkyl groups having 20 or less carbon atoms such as a butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and an alkyl group having 8 or less carbon atoms is preferable.
As X ₄ , a single bond, -COO-, or -CONH- is preferable, and a single bond or -COO- is more preferable.

The alkylene group for L _4, a methylene group, an ethylene group, a propylene group, butylene group, hexylene group, and is preferably an alkylene group having 1 to 8 carbon atoms such as octylene group.
As Ar ₄ , an aromatic ring group having 6 to 18 carbon atoms is preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are more preferable.

Hereinafter, specific examples of the repeating unit represented by the general formula (I) will be shown, but the present invention is not limited thereto. In the formula, a represents 1, 2 or 3.

(Repeating unit derived from hydroxystyrene (A-1))
The resin (A) preferably has a repeating unit (A-1) derived from hydroxystyrene as a repeating unit having an acid group.
Examples of the repeating unit (A-1) derived from hydroxystyrene include a repeating unit represented by the following general formula (1).

In general formula (1),
A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group or an aryloxycarbonyl group, and there are a plurality of them. In some cases, they may be the same or different. When having a plurality of Rs, they may form a ring jointly with each other. A hydrogen atom is preferable as R.
a represents an integer of 1 to 3, and b represents an integer of 0 to (5-a).

As the repeating unit (A-1), a repeating unit represented by the following general formula (AI) is preferable.

A resist composition containing a resin (A) having a repeating unit (A-1) is preferable for KrF exposure, EB exposure, or EUV exposure. In this case, the content of the repeating unit (A-1) is preferably 30 to 99 mol%, more preferably 40 to 99 mol%, and 50 to 99 mol% with respect to all the repeating units in the resin (A). Is more preferable.

(Repeating unit (A-2) having at least one selected from the group consisting of a lactone structure, a sultone structure, a carbonate structure, and a hydroxyadamantane structure)
The resin (A) may have a repeating unit (A-2) having at least one selected from the group consisting of a lactone structure, a carbonate structure, a sultone structure, and a hydroxyadamantane structure.

The lactone structure or sultone structure in the repeating unit having a lactone structure or sultone structure is not particularly limited, but a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable, and the 5- to 7-membered ring lactone structure is a bicyclo structure. , The other ring structure is fused in the form of forming a spiro structure, or the other ring structure is fused in the form of a bicyclo structure or a spiro structure in a 5- to 7-membered sultone structure. Is more preferable.
Examples of the repeating unit having a lactone structure or a sultone structure include the repeating units described in paragraphs 0094 to 0107 of WO2016 / 136354.

The resin (A) may have a repeating unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.
Examples of the repeating unit having a carbonate structure include the repeating unit described in paragraphs 0106 to 0108 of WO2019 / 054311.

The resin (A) may have a repeating unit having a hydroxyadamantane structure. Examples of the repeating unit having a hydroxyadamantane structure include a repeating unit represented by the following general formula (AIIA).

In the formula (AIIa), _{R 1} c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. R ₂ c to R ₄ c each independently represent a hydrogen atom or a hydroxyl group. However, _{at least one of R 2} c to R ₄ c represents a hydroxyl group. It is preferable that one or two of R ₂ c to R ₄ c are hydroxyl groups and the rest are hydrogen atoms.

(Repeating unit with fluorine atom or iodine atom)
The resin (A) may have a repeating unit having a fluorine atom or an iodine atom.
Examples of the repeating unit having a fluorine atom or an iodine atom include the repeating unit described in paragraphs 0080 to 0081 of JP-A-2019-045864.

(Repeating unit with photoacid generating group)
The resin (A) may have a repeating unit having a group that generates an acid by irradiation with radiation as a repeating unit other than the above.
Examples of the repeating unit having a fluorine atom or an iodine atom include the repeating unit described in paragraphs 0092 to 0906 of JP-A-2019-045864.

(Repeating unit with alkali-soluble group)
The resin (A) may have a repeating unit having an alkali-soluble group.
Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol in which the α-position is substituted with an electron-withdrawing group (for example, a hexafluoroisopropanol group). A carboxyl group is preferred. Since the resin (A) has a repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased.
The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit made of acrylic acid and methacrylic acid, or a repeating unit in which the alkali-soluble group is directly bonded to the main chain of the resin via a linking group. Repeat units to which an alkali-soluble group is attached can be mentioned. The linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure.
As the repeating unit having an alkali-soluble group, a repeating unit made of acrylic acid or methacrylic acid is preferable.

(Repeating unit having neither acid-degradable group nor polar group)
The resin (A) may further have a repeating unit that has neither an acid-degradable group nor a polar group. The repeating unit having neither an acid-decomposable group nor a polar group preferably has an alicyclic hydrocarbon structure.

Examples of the repeating unit having neither an acid-degradable group nor a polar group include the repeating unit described in paragraphs 0236 to 0237 of U.S. Patent Application Publication No. 2016/0026083, and the U.S. Patent Application Publication No. The repeating unit described in paragraph 0433 of the specification of 2016/0070167 is mentioned.

In addition to the above-mentioned repeating structural units, the resin (A) contains various repeating structural units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like. You may have.

(Characteristics of resin (A))
As the resin (A), it is preferable that all the repeating units are composed of repeating units derived from a (meth) acrylate-based monomer (a monomer having a (meth) acrylic group). In this case, any resin may be used: one in which all the repeating units are derived from a methacrylate-based monomer, one in which all the repeating units are derived from an acrylate-based monomer, and one in which all the repeating units are derived from a methacrylate-based monomer and an acrylate-based monomer. be able to. The repeating unit derived from the acrylate-based monomer is preferably 50 mol% or less based on all the repeating units in the resin (A).

When the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is for exposure to argon fluorohydride (ArF), the resin (A) is substantially aromatic from the viewpoint of the transmission of ArF light. It is preferable not to have a group group. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally, based on all the repeating units of the resin (A). Is more preferably 0 mol%, i.e. not having a repeating unit having an aromatic group.
Further, when the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is for ArF exposure, the resin (A) may have a monocyclic or polycyclic alicyclic hydrocarbon structure. It is preferable, and it is preferable that neither a fluorine atom nor a silicon atom is contained.

When the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is for krypton fluoride (KrF) exposure, EB exposure or EUV exposure, the resin (A) is an aromatic hydrocarbon group. It is preferable to have a repeating unit having a phenolic hydroxyl group, and more preferably to have a repeating unit having a phenolic hydroxyl group.
Examples of the repeating unit having a phenolic hydroxyl group include the repeating unit derived from hydroxystyrene (A-1) and the repeating unit derived from hydroxystyrene (meth) acrylate.
Further, when the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is for KrF exposure, EB exposure or EUV exposure, the resin (A) is a phenolic hydroxyl group hydrogen atom. It is also preferable to have a repeating unit having a structure protected by a group (leaving group) that decomposes and desorbs by the action of an acid.
When the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is for KrF exposure, EB exposure or EUV exposure, it has an aromatic hydrocarbon group contained in the resin (A). The content of the repeating unit is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, still more preferably 50 to 100 mol%, based on all the repeating units in the resin (A).

The resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
The weight average molecular weight (Mw) of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000. By setting the weight average molecular weight (Mw) of the resin (A) to 1,000 to 200,000, it is possible to prevent deterioration of heat resistance and dry etching resistance, and further, deterioration of developability and viscosity. It is possible to prevent the film from becoming high and deteriorating the film forming property. The weight average molecular weight (Mw) of the resin (A) is a polystyrene-equivalent value measured by the above-mentioned GPC method.
The dispersity (molecular weight distribution) of the resin (A) is usually 1 to 5, preferably 1 to 3, and more preferably 1.1 to 2.0. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side wall of the pattern, and the better the roughness.

In the actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention, the content of the resin (A) is preferably 50 to 99.9% by mass with respect to the total solid content of the composition. , 60-99.0% by mass is more preferable. Therefore, when the resin (A) is used as the resin to be put into the container in the step (1), the content of the resin (A) in the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is as described above. It is preferable to adjust the amount of the resin (A) added to the container in the step (1) so as to be within the range.
Further, the resin (A) may be used alone or in combination of two or more.
In addition, in this specification, a solid content means a component other than a solvent. Even if the properties of the above components are liquid, they are treated as solids. The total solid content means the sum of all the solid content.

[Surfactant]
The sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention may contain a surfactant (also referred to as "surfactant (E)"). By containing a surfactant, it is possible to form a pattern having better adhesion and fewer development defects.
The surfactant may be a resin or not a resin, but in the case of a resin, the surfactant is used as the "resin" that can be easily added in the step (1) of the production method of the present invention. be able to.
As the surfactant (E), a fluorine-based and / or silicon-based surfactant is preferable.
Examples of fluorine-based and / or silicon-based surfactants include the surfactants described in paragraph 0276 of US Patent Application Publication No. 2008/0248425. In addition, Ftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafuck F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Co., Ltd.); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troysol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); KH-20 (manufactured by Asahi Kasei Co., Ltd.); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (Manufactured by Neos Co., Ltd.) may be used. The polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

The surfactant (E) is a fluorocarbon produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method) in addition to the known surfactants as shown above. It may be synthesized using an aliphatic compound. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as the surfactant (H). This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-090991.
As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable, and the polymer is irregularly distributed. It may be a block copolymerized product. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, and a poly (oxybutylene) group, and poly (oxyethylene, oxypropylene, and oxyethylene). A unit having alkylenes having different chain lengths within the same chain length, such as poly (block conjugate of oxyethylene and oxypropylene), may be used. Further, the copolymer of the monomer having a fluoroaliphatic group and the (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer, but also a monomer having two or more different fluoroaliphatic groups. In addition, a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates) or the like may be used.
For example, as commercially available surfactants, Megafac F178, F-470, F- 473, F-475, F-476, F-472 ( manufactured by DIC _(Ltd.)), acrylates having a C _{6 F 13} group ( or methacrylate) and (poly (oxyalkylene)) acrylate (copolymer of or methacrylate), acrylate having a C ₃ F ₇ group (or methacrylate) (poly (oxyethylene) and) acrylate (or methacrylate) (poly (Oxypropylene)) Copolymer with acrylate (or methacrylate) can be mentioned.
In addition, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 may be used.

These surfactants (E) may be used alone or in combination of two or more.

When the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention contains a surfactant (E), the content of the surfactant (E) is the total solid content of the above composition. On the other hand, it is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass. Therefore, when the surfactant (E) is used as the resin to be put into the container in the step (1), the surfactant (E) in the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention It is preferable to adjust the amount of the surfactant (E) added to the container in the step (1) so that the content is within the above range.

[Hydrophobic resin]
The sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention may contain a hydrophobic resin (also referred to as “hydrophobic resin (F)”).
The hydrophobic resin (F) is a hydrophobic resin different from the above resin (A).
A hydrophobic resin (F) can be used as the "resin" to be put into the container in the step (1) of the production method of the present invention.
The hydrophobic resin (F) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and is a polar substance and a non-polar substance. Does not have to contribute to the uniform mixing of.
The effects of adding the hydrophobic resin (F) include controlling the static and dynamic contact angles of the resist film surface with respect to water, suppressing outgas, and the like.

Hydrophobic resin (F), from the viewpoint of uneven distribution in the film surface layer, "fluorine atom", "silicon atom", and, any one of "includes the CH ₃ moiety to the side chain portion of the resin" It is preferable to have the above, and it is more preferable to have two or more kinds. Further, the hydrophobic resin (F) preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted in the side chain.

When the hydrophobic resin (F) contains fluorine atoms and / or silicon atoms, the fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin, and may be contained in the side chain. It may be included.

When the hydrophobic resin (F) has a fluorine atom, the partial structure having a fluorine atom is preferably an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. ..
The alkyl group having a fluorine atom (preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. Further, it may have a substituent other than a fluorine atom.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than the fluorine atom.
Examples of the aryl group having a fluorine atom include a phenyl group and a group in which at least one hydrogen atom of an aryl group such as a naphthyl group is substituted with a fluorine atom, and further has a substituent other than the fluorine atom. May be good.
Examples of repeating units having a fluorine atom or a silicon atom include those exemplified in paragraph 0519 of US2012 / 0251948.

Further, as described above, it is also preferable that the hydrophobic resin (F) has a CH _{3-part structure in the side chain portion.}
Here, CH ₃ partial structure contained in the side chain portion in the hydrophobic resin comprises ethyl group, and a CH ₃ partial structure having a propyl group.
On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (F) (for example, the α-methyl group of a repeating unit having a methacrylic acid structure) is on the surface of the hydrophobic resin (F) due to the influence of the main chain. for contribution to uneven distribution is small, it shall not be included in the CH ₃ partial structures in the present invention.

Regarding the hydrophobic resin (F), the description in paragraphs 0348 to 0415 of JP2014-010245A can be referred to, and these contents are incorporated in the present specification.

As the hydrophobic resin (F), the resins described in JP-A-2011-248019, JP-A-2010-175859, and JP-A-2012-032544 can also be preferably used.

A preferred embodiment of the hydrophobic resin (F) is a resin having a repeating unit represented by the following general formula (F-1).

In the general formula (F-1), RF ₁ represents a hydrogen atom or an alkyl group, and RF ₂ represents an alkyl group, a cycloalkyl group or an aryl group.
The alkyl group as RF ₁ may be linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms. preferable.
The alkyl group as RF ₂ may be linear or branched, preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 5 to 25 carbon atoms, and further preferably an alkyl group having 6 to 20 carbon atoms. preferable. The alkyl group as RF ₂ preferably has a substituent containing a fluorine atom or a silicon atom.
The cycloalkyl group as RF ₂ may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 30 carbon atoms, more preferably a cycloalkyl group having 5 to 25 carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms. Groups are even more preferred. The cycloalkyl group as RF ₂ preferably has a substituent containing a fluorine atom or a silicon atom.
The aryl group as RF ₂ is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 25 carbon atoms, and even more preferably an aryl group having 6 to 20 carbon atoms. The aryl group as RF ₂ preferably has a substituent containing a fluorine atom or a silicon atom.

When the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention contains the hydrophobic resin (F), the content of the hydrophobic resin (F) is the total solid content of the composition. On the other hand, it is preferably 0.01 to 20% by mass, and more preferably 0.1 to 15% by mass. Therefore, when the hydrophobic resin (F) is used as the resin to be put into the container in the step (1), the hydrophobic resin (F) in the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention. It is preferable to adjust the amount of the hydrophobic resin (F) added to the container in the step (1) so that the content is within the above range.

<Compounds that generate acid by irradiation with active light or radiation (photoacid generator)>
A compound that generates an acid by irradiation with active light or radiation (also referred to as “photoacid generator (C)”) will be described.
The photoacid generator (C) is not particularly limited as long as it is a compound that generates an acid by being irradiated with active light or radiation.
The photoacid generator (C) may be in the form of a small molecule compound or may be incorporated in a part of the polymer. Further, the form of the small molecule compound and the form incorporated in a part of the polymer may be used in combination.
When the photoacid generator (C) is in the form of a small molecule compound, the weight average molecular weight (Mw) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less. ..
The photoacid generator (C) may be incorporated in a part of the resin (A), or may be incorporated in a resin different from the resin (A).
The photoacid generator (C) is preferably in the form of a small molecule compound.

The photoacid generator (C) is preferably a compound that generates an organic acid by irradiation with active light or radiation, a compound that generates an organic acid by irradiation with active light or radiation, and a fluorine atom in the molecule. Alternatively, it is more preferably a compound having an iodine atom. Examples of the organic acid include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphor sulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkylcarboxylic acid, etc.), and the like. Examples thereof include carbonylsulfonylimide acid, bis (alkylsulfonyl) imide acid, and tris (alkylsulfonyl) methidoic acid.

Preferable embodiments of the photoacid generator (C) include, for example, a compound represented by the following general formula (ZI), a compound represented by the following general formula (ZII), and a compound represented by the following general formula (ZIII). Examples include compounds.

In the above general formula (ZI)
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The _{number of carbon atoms of the organic group as R 201} , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ ~ _{R 203,} an alkylene group (e.g., butylene, pentylene) and _{_{_{-CH 2 -CH 2 -O-CH 2}}} -CH 2 - and the like can.
Z ^- represents an anion.

(Cation in the compound represented by the general formula (ZI))
Preferable embodiments of the cation in the general formula (ZI) include the corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.
The photoacid generator (C) may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of _R 201 _{~ R 203} of the compound represented by formula (ZI), and at least one of _R 201 _{~ R 203} of another compound represented by formula (ZI), a single bond Alternatively, it may be a compound having a structure bonded via a linking group.

(Compound (ZI-1))
First, the compound (ZI-1) will be described.
The compound (ZI-1) is an _{aryl sulfonium compound in which at least one of R 201} to R ₂₀₃ of the above general formula (ZI) is an aryl group, that is, a compound having an aryl sulfonium as a cation.
In the aryl sulfonium compound _{, all of R 201} to R ₂₀₃ may be an aryl group, or _{a part of R 201} to R ₂₀₃ may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.
Examples of the aryl sulfonium compound include a triaryl sulfonium compound, a diallyl alkyl sulfonium compound, an aryl dialkyl sulfonium compound, a diallyl cycloalkyl sulfonium compound, and an aryl dicycloalkyl sulfonium compound.

As the aryl group of the aryl sulfonium compound, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues and the like. When the aryl sulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group contained in the arylsulfonium compound as required is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms. The group is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ are independently an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), and an aryl group (for example, carbon number of carbon atoms). 6 to 14), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be used as a substituent.

(Compound (ZI-2))
Next, the compound (ZI-2) will be described.
The compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in the general formula (ZI) each independently represent an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom.
The _{organic group having no aromatic ring as R 201} to R ₂₀₃ generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
Each of R ₂₀₁ to R ₂₀₃ is independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and more preferably a linear or branched 2-oxoalkyl group or 2-oxocycloalkyl group. Alternatively, it is an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.). Butyl group and pentyl group), and cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group) can be mentioned.
R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

(Compound (ZI-3))
Next, the compound (ZI-3) will be described.
The compound (ZI-3) is represented by the following general formula (ZI-3) and has a phenacylsulfonium salt structure.

Even if any two or more of _{R 1c} to R _5c _{, R 5c} and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y are combined to form a ring structure, respectively. Often, this ring structure may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings in which two or more of these rings are combined. Examples of the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

_{Examples of} the group formed by combining any two or more of R 1c to R _5c _{, R 6c} and R _7c , and R _x and R _y include a butylene group and a pentylene group.
The _{group formed by bonding R 5c} and R _6c , and R _5c and R _x is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

The alkyl groups as R _6c and R _7c are not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 15 carbon atoms. Is more preferable, and an alkyl group having 1 to 10 carbon atoms is further preferable.
The alkyl group may have a substituent.

The cycloalkyl group as R _6c and R _7c is not particularly limited, but may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkyl group having 3 to 15 carbon atoms. It is more preferable to have a cycloalkyl group having 3 to 10 carbon atoms.
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthalenyl group.
The cycloalkyl group may have a substituent.

The aryl groups as R _6c and R _7c are not particularly limited, but may be monocyclic or polycyclic, preferably an aryl group having 6 to 20 carbon atoms, and preferably an aryl group having 6 to 15 carbon atoms. More preferably, it is an aryl group having 6 to 10 carbon atoms.
The aryl group may have a substituent.

R _6c and R _7c are each independently preferably a hydrogen atom, an alkyl group, or a cycloalkyl group, and more preferably a hydrogen atom or an alkyl group.

_{The alkyl groups as RX} and R _y are not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 15 carbon atoms. Is more preferable, and an alkyl group having 1 to 10 carbon atoms is further preferable.
The alkyl group may have a substituent.

The cycloalkyl group as R _X and R _y is not particularly limited, may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms It is more preferable to have a cycloalkyl group having 3 to 10 carbon atoms.
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthalenyl group.
The cycloalkyl group may have a substituent.

_{The 2-oxoalkyl group as RX} and _Ry is not particularly limited, but is preferably a 2-oxoalkyl group having 1 to 20 carbon atoms, and is a 2-oxoalkyl group having 1 to 15 carbon atoms. Is more preferable, and a 2-oxoalkyl group having 1 to 10 carbon atoms is further preferable.
The 2-oxoalkyl group may have a substituent.

_{The 2-oxocycloalkyl group as RX} and _Ry is not particularly limited, but is preferably a 2-oxocycloalkyl group having 3 to 20 carbon atoms, and a 2-oxocycloalkyl group having 3 to 15 carbon atoms. It is more preferable that it is a 2-oxocycloalkyl group having 3 to 10 carbon atoms.
The 2-oxocycloalkyl group may have a substituent.

Alkoxycarbonylalkyl group as R _X and R _y is not particularly limited, but is preferably an alkoxycarbonylalkyl group having 3 to 22 carbon atoms, more preferably an alkoxycarbonyl group having 3 to 17 carbon atoms , It is more preferably an alkoxycarbonylalkyl group having 3 to 12 carbon atoms.
The alkoxycarbonylalkyl group may have a substituent.

_RX and R _y may be linked to each other to form a ring, and this ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, and an amide bond.
The ring structure preferably contains an oxygen atom.
Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings in which two or more of these rings are combined. Examples of the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

(Compound (ZI-4))
Next, the compound (ZI-4) will be described.
The compound (ZI-4) is represented by the following general formula (ZI-4).

In the general formula (ZI-4),
l represents an integer of 0 to 2.
r represents an integer from 0 to 8.
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxycarbonyl group.
R ₁₄ represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a cycloalkylsulfonyl group. When _{a plurality of R 14s} exist, they may be the same or different.
Each of R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Bonded to two R ₁₅ each other may form a ring. When two R ₁₅ are combined to form a ring together, it may contain a hetero atom in the ring skeleton.
Z ^- represents an anion.

In the general formula (ZI-4), _{the alkyl groups of R 13} , R ₁₄ and R ₁₅ are linear or branched, preferably those having 1 to 10 carbon atoms, and are methyl group, ethyl group and n-. A butyl group, a t-butyl group, or the like is more preferable.

The alkyl group as R ₁₃ is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 15 carbon atoms. , An alkyl group having 1 to 10 carbon atoms is more preferable, and specifically, a methyl group, an ethyl group, an n-butyl group, or a t-butyl group is preferable.
The alkyl group may have a substituent.

The cycloalkyl group as R ₁₃ is not particularly limited, but may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, and preferably a cycloalkyl group having 3 to 15 carbon atoms. More preferably, it is a cycloalkyl group having 3 to 10 carbon atoms.
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthalenyl group.
The cycloalkyl group may have a substituent.

The alkoxy group as R ₁₃ is not particularly limited, but is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. Is more preferable.
The alkoxy group may have a substituent.

The alkoxycarbonyl group as R ₁₃ is not particularly limited, but is preferably an alkoxycarbonyl group having 2 to 21 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 16 carbon atoms, and 2 to 11 carbon atoms. It is more preferable that it is an alkoxycarbonyl group of.
The alkoxycarbonyl group may have a substituent.

The alkyl group as R ₁₄ is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 15 carbon atoms. , An alkyl group having 1 to 10 carbon atoms is more preferable, and specifically, a methyl group, an ethyl group, an n-butyl group, or a t-butyl group is preferable.
The alkyl group may have a substituent.

The cycloalkyl group as R ₁₄ is not particularly limited, but may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, and preferably a cycloalkyl group having 3 to 15 carbon atoms. More preferably, it is a cycloalkyl group having 3 to 10 carbon atoms.
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthalenyl group.
The cycloalkyl group may have a substituent.

The alkoxy group as R ₁₄ is not particularly limited, but is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. Is more preferable.
The alkoxy group may have a substituent.

The alkoxycarbonyl group as R ₁₄ is not particularly limited, but is preferably an alkoxycarbonyl group having 2 to 21 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 16 carbon atoms, and 2 to 11 carbon atoms. It is more preferable that it is an alkoxycarbonyl group of.
The alkoxycarbonyl group may have a substituent.

The _{alkylcarbonyl group as R 14} is not particularly limited, but is preferably an alkylcarbonyl group having 2 to 21 carbon atoms, more preferably an alkylcarbonyl group having 2 to 16 carbon atoms, and 2 to 11 carbon atoms. It is more preferable that it is an alkylcarbonyl group of.
The alcoholylcarbonyl group may have a substituent.

The alkylsulfonyl group as R ₁₄ is not particularly limited, but is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, more preferably an alkylsulfonyl group having 1 to 15 carbon atoms, and 1 to 10 carbon atoms. It is more preferably the alkylsulfonyl group of.
The alkylsulfonyl group may have a substituent.

The cycloalkylsulfonyl group as R ₁₄ is not particularly limited, but is preferably a cycloalkylsulfonyl group having 3 to 20 carbon atoms, more preferably a cycloalkylsulfonyl group having 3 to 15 carbon atoms, and has a carbon number of 3 to 15. It is more preferably 3 to 10 cycloalkylsulfonyl groups.
The cycloalkylsulfonyl group may have a substituent.

R ₁₄ is, if there are two or more, plural R ₁₄ may being the same or different.

The alkyl group as R ₁₅ is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 15 carbon atoms. , An alkyl group having 1 to 10 carbon atoms is more preferable, and specifically, a methyl group, an ethyl group, an n-butyl group, or a t-butyl group is preferable.
The alkyl group may have a substituent.

The cycloalkyl group as R ₁₅ is not particularly limited, may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, be a cycloalkyl group having 3 to 15 carbon atoms More preferably, it is a cycloalkyl group having 3 to 10 carbon atoms.
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthalenyl group.
The cycloalkyl group may have a substituent.

The naphthyl group as R ₁₅ may have a substituent.

Bonded to two R ₁₅ each other may form a ring. When two R ₁₅ are combined to form a ring; and the ring structure may contain an oxygen atom, a sulfur atom, it may contain a hetero atom such as nitrogen atom, oxygen atom, nitrogen atom, a sulfur atom, a ketone group , Ether bond, ester bond, amide bond may be included.
The ring structure preferably contains an oxygen atom.
Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings in which two or more of these rings are combined. Examples of the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

In a preferred embodiment, two R ₁₅ is an alkyl group, it is preferable to form a ring structure.

(Cation in the compound represented by the general formula (ZII) or the general formula Z (III))
Next, the general formulas (ZII) and (ZIII) will be described.
In the general formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
As _{the aryl group of R 204} to R _207, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.). Butyl group and pentyl group), cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group) can be mentioned.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R _{207 may each have an independent substituent.} Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 to 15 carbon atoms). 15), aryl groups (for example, 6 to 15 carbon atoms), alkoxy groups (for example, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like can be mentioned.
Z ^- represents an anion.

(Anion in a compound represented by the general formula (ZI), the general formula (ZII), the general formula (ZI-3), or the general formula (ZI-4))
Z in the general formula (ZI) ^-, Z in the general formula (ZII) ^-, Zc in formula (ZI-3) ^-, and Z in the general formula (ZI-4) ^- as the following general formula (3) The represented anion is preferred.

In general formula (3),
o represents an integer of 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.
Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of them, R ₄ and R ₅ are the same, respectively. But it may be different.
L represents a divalent linking group, and when there are a plurality of L, the L may be the same or different.
W represents an organic group.
o represents an integer of 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More preferably, Xf is a fluorine atom or CF _3. In particular, it is preferable that both Xfs are fluorine atoms.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are a plurality of R ₄ and R ₅ , they may be the same or different from each other.
The alkyl group as R ₄ and R ₅ may have a substituent, and preferably has 1 to 4 carbon atoms. R ₄ and R ₅ are preferably hydrogen atoms.
Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in the general formula (3).

L represents a divalent linking group, and when there are a plurality of L, the L may be the same or different.
Examples of the divalent linking group include -COO- (-C (= O) -O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-,-. SO-, -SO _2- , alkylene group (preferably 1 to 6 carbon atoms), cycloalkylene group (preferably 3 to 15 carbon atoms), alkenylene group (preferably 2 to 6 carbon atoms), and a combination thereof. Examples include a divalent linking group. Among them, -COO -, - OCO -, - CONH -, - NHCO -, - CO -, - O -, - SO 2 -, - COO- alkylene group -, - OCO- alkylene group -, - CONH- alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.

W represents an organic group.
The number of carbon atoms of the organic group is not particularly limited, but is generally 1 to 30, preferably 1 to 20.
The organic group is not particularly limited, but represents, for example, an alkyl group, an alkoxy group, or the like.
The alkyl group is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. More preferred.
The alkyl group and the alkoxy group may have a substituent. It may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T, and a fluorine atom is preferable.

W preferably represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferable.
Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
The alicyclic group may be a monocyclic type or a polycyclic type. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Of these, alicyclic groups having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferable.

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group and an anthryl group.
The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can suppress the diffusion of acid more. Further, the heterocyclic group may or may not have aromaticity. Examples of the aromatic heterocycle include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the non-aromatic heterocycle include a tetrahydropyran ring, a lactone ring, a sultone ring and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the above-mentioned resin. As the heterocycle in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.

The cyclic organic group may have a substituent. The substituent may be, for example, an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms) and a cycloalkyl group (which may be monocyclic, polycyclic or spirocyclic). Often, 3 to 20 carbon atoms are preferable), an aryl group (preferably 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid. Examples include ester groups. The carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be a carbonyl carbon.

Preferred examples of the sulfonium cation in the general formula (ZI) and the iodonium cation in the general formula (ZII) are shown below.

Preferred examples of the general formula (ZI), the anion Z ^{− in} the general formula (ZII), the Zc ⁻ ^{in the general formula (ZI-3), and the Z − in} the general formula (ZI-4) are shown below.

The above cations and anions can be arbitrarily combined and used as a photoacid generator.
In the present invention, the compound that generates an acid by irradiation with active light or radiation is at least one selected from the compound represented by the general formula (ZI-3) and the compound represented by the general formula (ZI-4). It is preferably a seed.

As the photoacid generator (C), a compound represented by the following general formula (iP) can also be used.

In the general formula (iP), R ₁₀₁ to R ₁₀₆ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, respectively.

The alkyl group as R ₁₀₁ to R ₁₀₆ is not particularly limited, but may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 15 carbon atoms. Is more preferable, and an alkyl group having 1 to 10 carbon atoms is further preferable.
The alkyl group may have a substituent.

The cycloalkyl group as R ₁₀₁ to R ₁₀₆ is not particularly limited, but may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkyl group having 3 to 15 carbon atoms. It is more preferable to have a cycloalkyl group having 3 to 10 carbon atoms.
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthalenyl group.
The cycloalkyl group may have a substituent.

The aryl group as R ₁₀₁ to R ₁₀₆ is not particularly limited, but may be monocyclic or polycyclic, preferably an aryl group having 6 to 20 carbon atoms, and preferably an aryl group having 6 to 15 carbon atoms. More preferably, it is an aryl group having 6 to 10 carbon atoms.
The aryl group may have a substituent.

^{The volume of the acid generated by the photoacid generator (C) is not particularly limited, but 240 Å 3} or more is preferable from the viewpoint of suppressing the diffusion of the acid generated by exposure to the unexposed portion and improving the resolution. , 305 Å ³ or more is more preferable, 350 Å ³ or more is further preferable, and 400 Å ³ or more is particularly preferable. Incidentally, from the viewpoint of solubility in sensitivity or coating solvent, the volume of the acid generated from the photoacid generator (C) is preferably 1500 Å ³ or less, 1000 Å ^3, more preferably less, 700 Å ³ or less is more preferable.
The above volume value is obtained using "WinMOPAC" manufactured by Fujitsu Limited. In calculating the volume value, first, the chemical structure of the acid is input, and then the most stable conformation of each acid is calculated by molecular mechanics using the MM (Molecular Mechanics) 3 method with this structure as the initial structure. The conformation is determined, and then the "accessible volume" of each acid can be calculated by performing molecular orbital calculation using the PM (Parameterized Model number) 3 method for these most stable conformations.

The structure of the acid generated by the photoacid generator (C) is not particularly limited, but the acid and resin generated by the photoacid generator (C) in terms of suppressing the diffusion of the acid and improving the resolution (C) It is preferable that the interaction with A) is strong. From this point of view, when the acid generated by the photoacid generator (C) is an organic acid, an organic acid group (for example, a sulfonic acid group, a carboxylic acid group, a carbonylsulfonylimide acid group, a bissulfonylimide acid group, a trissulfonyl) It is preferable to have a polar group in addition to the methylic acid group).
Examples of the polar group include an ether group, an ester group, an amide group, an acyl group, a sulfo group, a sulfonyloxy group, a sulfonamide group, a thioether group, a thioester group, a urea group, a carbonate group, a carbamate group, a hydroxyl group and a mercapto. The group etc. can be mentioned.
The number of polar groups contained in the acid generated by the photoacid generator (C) is not particularly limited, and is preferably 1 or more, and more preferably 2 or more. However, from the viewpoint of suppressing excessive development, the number of polar groups is preferably less than 6, more preferably less than 5, and even more preferably less than 4.

Above all, the photoacid generator (C) is preferably a photoacid generator composed of an anion portion and a cation portion because the effect of the present invention is more excellent.
Examples of the photoacid generator (C) include the photoacid generator described in paragraphs 0144 to 0173 of JP-A-2019-045864.

In the actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention, the content of the photoacid generator (C) is 0.1 to 20 mass by mass with respect to the total solid content of the composition. % Is preferable, 0.5 to 15% by mass is more preferable, and 1.0 to 10% by mass is further preferable. Therefore, the light to be put into the container in the step (1) so that the content of the photoacid generator (C) in the actinic cheilitis or radiation-sensitive resin composition produced by the production method of the present invention is within the above range. It is preferable to adjust the amount of the acid generator (C) added.

The photoacid generator (C) may be used alone or in combination of two or more. When two or more photoacid generators (C) are used in combination, the total amount thereof is preferably within the above range.

<Acid diffusion control agent (D)>
An acid diffusion control agent (also referred to as “acid diffusion control agent (D)”) will be described.
The acid diffusion control agent (D) traps the acid generated from the photoacid generator (C) or the like at the time of exposure, and causes the reaction of the resin (A) (acid-degradable resin) in the unexposed portion by the excess generated acid. It acts as a suppressive quencher.
Examples of the acid diffusion control agent (D) include a basic compound (DA), a basic compound (DB) whose basicity is reduced or eliminated by irradiation with active light or radiation, and a photoacid generator (C). Onium salt (DC) which is a relatively weak acid, low molecular weight compound (DD) which has a nitrogen atom and has a group which is eliminated by the action of acid, and onium salt compound (DE) which has a nitrogen atom in the cation part. ) Etc. can be used.
In the present invention, a known acid diffusion control agent can be appropriately used. For example, paragraphs [0627] to [0664] of US Patent Application Publication No. 2016/0070167, paragraphs [0995] to [0187] of US Patent Application Publication No. 2015/0004544, US Patent Application Publication No. 2016/0237190. Known compounds disclosed in paragraphs [0403] to [0423] of the specification and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458 are used as the acid diffusion control agent (D). Can be preferably used.

Examples of the basic compound (DA) include the compounds described in paragraphs 0188 to 0208 of JP-A-2019-045864.

In the present invention, an onium salt (DC), which is a weak acid relative to the photoacid generator (C), can also be used as the acid diffusion control agent (D).
When the photoacid generator (C) and the onium salt that generates an acid that is relatively weak acid with respect to the acid generated from the photoacid generator (C) are mixed and used, the active light or radiation When the acid generated from the photoacid generator (C) by irradiation collides with an onium salt having an unreacted weak acid anion, the weak acid is released by salt exchange to produce an onium salt having a strong acid anion. In this process, the strong acid is exchanged for the weak acid with lower catalytic ability, so it is considered that the acid is apparently inactivated and the acid diffusion can be controlled.

Examples of the onium salt that is relatively weak acid with respect to the photoacid generator (C) include the onium salt described in paragraphs 0224 to 0233 of JP-A-2019-070676.

As the basic compound (DA), preferably, a compound having a structure represented by the following formulas (A) to (E) can be mentioned.

In the general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and each independently has a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms), and an aryl. Group (preferably 6 to 20 carbon atoms), alkylcarbonyl group (preferably 2 to 21 carbon atoms), cycloalkylcarbonyl group (preferably 4 to 21 carbon atoms), arylcarbonyl group (preferably 7 to 21 carbon atoms) , An alkylsulfonyl group (preferably 1 to 20 carbon atoms), a cycloalkylsulfonyl group (preferably 3 to 20 carbon atoms), or an arylsulfonyl group (preferably 6 to 20 carbon atoms). At ^{least two of R 200} , R ²⁰¹ and R ²⁰² may be bonded to form a ring, and at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, a carbonyl group and a sulfonyl group may be formed in the ring. May include one.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

Regarding the above alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.
It is more preferable that the alkyl groups in the general formulas (A) and (E) are unsubstituted.

As the basic compound (DA), guanidine, aminopyrrolidin, pyrazole, pyrazoline, piperazin, aminomorpholine, aminoalkylmorpholin, piperidine and the like are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, etc. A compound having a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, and the like are more preferable.

A basic compound (DB) whose basicity is reduced or eliminated by irradiation with active light or radiation (hereinafter, also referred to as “compound (DB)”) has a proton acceptor functional group and is active light or It is a compound that is decomposed by irradiation with radiation to reduce or disappear its proton accepting property, or to change from proton accepting property to acidic.

A proton-accepting functional group is a functional group having a group or an electron capable of electrostatically interacting with a proton, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a π-conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

Preferred partial structures of the proton acceptor functional group include, for example, crown ethers, aza-crown ethers, primary to tertiary amines, pyridines, imidazoles, and pyrazine structures.

The compound (DB) is decomposed by irradiation with active light or radiation to reduce or eliminate the proton acceptor property, or generate a compound in which the proton acceptor property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group, and is specific. Means that when a proton adduct is formed from a compound (DB) having a proton-accepting functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
Proton acceptability can be confirmed by measuring pH.

The acid dissociation constant pKa of the compound generated by decomposing the compound (DB) by irradiation with active light or radiation preferably satisfies pKa <-1, more preferably -13 <pKa <-1, and -13 <pKa. <-3 is more preferable.

The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined in, for example, Chemical Handbook (II) (Revised 4th Edition, 1993, edited by Japan Chemical Society, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the higher the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can be used to calculate Hammett's substituent constants and values based on a database of publicly known literature values. All pKa values described herein indicate values calculated using this software package.

Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

In the composition of the present invention, an onium salt (DC), which is a weak acid relative to the acid generator, can be used as the acid diffusion control agent.
When an acid generator and an onium salt that generates an acid, which is a weak acid relative to the acid generated from the acid generator, are mixed and used, the acid generator is generated by active light or irradiation with radiation. When an acid collides with an onium salt having an unreacted weak acid anion, salt exchange releases the weak acid to produce an onium salt with a strong acid anion. In this process, the strong acid is exchanged for the weak acid having a lower catalytic ability, so that the acid is apparently inactivated and the acid diffusion can be controlled.

The onium salt, which is a weak acid relative to the acid generator, is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

In the formula, R ⁵¹ is a hydrocarbon group which may have a substituent, and Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, carbon adjacent to S). R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or arylene group, and Rf is a fluorine atom. It is a hydrocarbon group containing, and M ⁺ is independently an ammonium cation, a sulfonium cation or an iodonium cation.

Preferred examples of the sulfonium cation or iodonium cation represented by M ⁺ include the sulfonium cation exemplified by the general formula (ZI) and the iodonium cation exemplified by the general formula (ZII).

The onium salt (DC), which is a weak acid relative to the acid generator, is a compound having a cation moiety and an anion moiety in the same molecule, and the cation moiety and anion moiety are linked by a covalent bond ( Hereinafter, it may also be referred to as “compound (DCA)”).
The compound (DCA) is preferably a compound represented by any of the following general formulas (C-1) to (C-3).

In the general formulas (C-1) to (C-3),
R ₁ , R ₂ , and R ₃ each independently represent a substituent having one or more carbon atoms.
L ₁ represents a divalent linking group or a single bond that links the cation site and the anion site.
-X ^- ^_is, -COO ^-, ^-SO 3 - represents an anion portion selected from -R ₄ ^-, -SO ₂ -, and ^-N. R ₄ is a linking site with the adjacent N atom, a carbonyl group (-C (= O) -) , sulfonyl group _{(-S (= O) 2 -} ), and sulfinyl group (-S (= O) - ) Represents a monovalent substituent having at least one of them.
R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be combined with each other to form a ring structure. Further, in the general formula (C-3), two of R ₁ to R ₃ are combined to represent one divalent substituent, which may be bonded to an N atom by a double bond.

Substituents having 1 or more carbon atoms in R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino. Examples thereof include a carbonyl group and an arylaminocarbonyl group. It is preferably an alkyl group, a cycloalkyl group, or an aryl group.

_{L 1} as a divalent linking group includes a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and two kinds thereof. Examples thereof include groups formed by combining the above. L ₁ is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

A small molecule compound (DD) having a nitrogen atom and having a group desorbed by the action of an acid (hereinafter, also referred to as “compound (DD)”) has a group desorbed by the action of an acid on the nitrogen atom. It is preferably an amine derivative having.
As the group desorbed by the action of the acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminoal ether group is preferable, and a carbamate group or a hemiaminol ether group is more preferable. ..
The molecular weight of compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.
Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In the general formula (d-1)
Rb is independently a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), and an aralkyl group (preferably 3 to 30 carbon atoms). It preferably represents 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb may be connected to each other to form a ring.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are independently hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups and other functional groups, alkoxy groups, or alkyl groups. It may be substituted with a halogen atom. The same applies to the alkoxyalkyl group indicated by Rb.

As Rb, a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable.
Examples of the ring formed by connecting the two Rbs to each other include an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocyclic hydrocarbon and a derivative thereof.
Specific structures of the group represented by the general formula (d-1) include, but are not limited to, the structure disclosed in paragraph [0466] of the US Patent Publication No. US2012 / 0135348A1. ..

The compound (DD) preferably has a structure represented by the following general formula (6).

In the general formula (6)
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two Ras may be the same or different, and the two Ras may be interconnected to form a heterocycle with the nitrogen atom in the equation. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
Rb has the same meaning as Rb in the above general formula (d-1), and the same applies to preferred examples.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra are independently substituted with the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb, respectively. As a good group, it may be substituted with a group similar to the group described above.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra (these groups may be substituted with the above group) include groups similar to the above-mentioned specific examples for Rb. Be done.
Specific structures of the particularly preferred compound (DD) in the present invention include, but are limited to, the compounds disclosed in paragraph [0475] of U.S. Patent Application Publication No. 2012/01335348A1. is not it.

The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter, also referred to as “compound (DE)”) is preferably a compound having a basic moiety containing a nitrogen atom in the cation portion. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is more preferable that all the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that an electron-attracting functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly bonded to the nitrogen atom.
Preferred specific structures of compound (DE) include, but are not limited to, the compounds disclosed in paragraph [0203] of US Patent Application Publication 2015/0309408A1.

In the actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention, the content of the acid diffusion control agent (D) (the total of a plurality of types, if present) is determined by the total solid content of the composition. On the other hand, 0.1 to 10.0% by mass is preferable, and 0.1 to 5.0% by mass is more preferable. Therefore, the acid to be put into the container in the step (1) so that the content of the acid diffusion control agent (D) in the actinic cheilitis or radiation-sensitive resin composition produced by the production method of the present invention is within the above range. It is preferable to adjust the amount of the diffusion control agent (D) added.
In the present invention, the acid diffusion control agent (D) may be used alone or in combination of two or more.

<Solvent>
A solvent (also referred to as “solvent (S)”) will be described.
The solvent (S) includes (M1) propylene glycol monoalkyl ether carboxylate, and (M2) propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and. It preferably contains at least one selected from the group consisting of alkylene carbonates. The solvent in this case may further contain components other than the components (M1) and (M2).
When the solvent containing the component (M1) or (M2) is used in combination with the above-mentioned resin (A), the coatability of the actinic cheilitis or radiation-sensitive resin composition is improved, and the number of development defects is small. This is preferable because a pattern can be formed.

The solvent (S) includes, for example, an alkylene glycol monoalkyl ether carboxylate, an alkylene glycol monoalkyl ether, a lactate alkyl ester, an alkyl alkoxypropionate, a cyclic lactone (preferably having 4 to 10 carbon atoms), and a ring. Examples thereof include organic solvents such as a monoketone compound (preferably having 4 to 10 carbon atoms), an alkylene carbonate, an alkyl alkoxyacetate, and an alkyl pyruvate.

In the actinic cheilitis or radiation-sensitive resin composition produced by the production method of the present invention, the content of the solvent (S) is adjusted so that the solid content concentration of the composition is 0.5 to 40% by mass. It is preferable that the amount is adjusted to 3 to 30% by mass. In particular, in that the effect of the present invention is more excellent, the solid content concentration of the actinic cheilitis or radiation-sensitive resin composition produced by the production method of the present invention is preferably 10% by mass or more, preferably 10 to 30% by mass. Most preferably. Therefore, the amount of the solvent (S) to be added to the container in the step (1) is adjusted so that the solid content concentration of the actinic cheilitis or radiation-sensitive resin composition produced by the production method of the present invention is within the above range. It is preferable to do so. The solid content concentration is the mass of the mass of other components (components that can constitute the actinic cheilitis or radiation-sensitive film) other than the solvent with respect to the total mass of the actinic cheilitis or radiation-sensitive resin composition. Means percentage.

In the production method of the present invention, in step (1), in addition to the above resin, photoacid generator (C), acid diffusion control agent (D), and solvent (S), other components other than these are placed in a container. It may be added. Examples of other components include cross-linking agents, alkali-soluble resins, dissolution-inhibiting compounds, dyes, plasticizers, photosensitizers, light absorbers, compounds that promote solubility in developers, and the like.
The other components may be added into the container in the step (1), or may be added in a step other than the step (1) instead of the step (1).

<Process (1-2)>
The production method of the present invention is performed between steps (1) and (2).
It is preferable to have the step (1-2) of mixing the resin, the photoacid generator, the acid diffusion control agent, and the solvent in the container in the step (1).
In the step (1-2), in addition to the resin, the photoacid generator, the acid diffusion control agent, and the solvent contained in the container in the step (1), other components may be further mixed.
The mixing method in the step (1-2) is not particularly limited, but for example, it is preferable to stir and mix with the above-mentioned stirring blade.
Step (1-2) starts after step (1) is completed.
The step (1-2) may be continuously performed with the above-mentioned step (1) (the step (1-2) may be started at the same time as the step (1) is completed), and the step (1) After that, the step (1-2) may be started after a while, but from the viewpoint of productivity, it is preferable to start the step (1) continuously.
Further, when the resin, the photoacid generator, the acid diffusion control agent, and the solvent are put into the container in the step (1), the stirring blade in the container is operated, and at the same time when all the above components are put into the container ( Step (1-2) may be started (that is, the inside of the container may be continuously stirred from the start of step (1) to the end of step (1-2)). ..

The mixing time in the step (1-2) (that is, the time for performing the step (1-2)) is not particularly limited, but is preferably 30 minutes or more, more preferably 1 hour or more, and 2 hours or more. It is more preferably 4 hours or more, and particularly preferably 8 hours or more. By setting the mixing time to 30 minutes or more, it is considered that the agglutinating state of the materials is stabilized and the effect of the present invention is more easily exhibited. The upper limit of the mixing time is not particularly limited, but from the viewpoint of productivity, it is preferably 24 hours or less, more preferably 18 hours or less, and further preferably 12 hours or less.

The temperature at the time of mixing (the temperature of the contents in the container) is not particularly limited, but is preferably 15 to 32 ° C, more preferably 20 to 24 ° C.
Further, when mixing, the temperature of the contents in the container is preferably kept constant, preferably within ± 10 ° C., more preferably within ± 5 ° C., and even more preferably within ± 1 ° C. from the set temperature. ..
The rotation speed of the stirring blade during stirring and mixing is not particularly limited, but is preferably 20 to 500 rpm (rotations per minute), more preferably 40 to 350 rpm, and even more preferably 50 to 300 rpm.
When stopping the mixing, it is preferable to confirm that each component is dissolved or uniformly dispersed in the solvent.
At the time of mixing, ultrasonic waves may be applied to the contents in the container.

<Process (2)>
In the step (2), at least one of the resin, the photoacid generator, the acid diffusion control agent, and the solvent is placed in a container containing the resin, the photoacid generator, the acid diffusion control agent, and the solvent. Is the process of adding.

In the present invention, the step (2) is performed after the step (1) is completed, but it is preferable to perform the step (2) 30 minutes or more after the step (1) is completed.
Between step (1) and step (2), it is preferable to leave 30 minutes or more, more preferably 1 hour or more, further preferably 2 hours or more, further preferably 4 hours or more, and 8 hours. It is particularly preferable to leave the above space. It is considered that the agglutination state between the materials is stabilized and the effect of the present invention is more easily exhibited by leaving a space between the steps (1) and the steps (2) for 30 minutes or more. The upper limit of the time between the steps (1) and the step (2) is not particularly limited, but is preferably 48 hours or less, more preferably 36 hours or less, and 24 hours or less from the viewpoint of productivity. Is even more preferable.

In the present invention, it is preferable that the step (1-2) is performed after the step (1), and then the step (2) is performed.
The step (2) may be continuously performed with the above-mentioned step (1-2), or may be performed after a time after the step (1-2).
When the step (1-2) and the step (2) are continuously performed, when the step (2) is started (that is, in a container containing a resin, a photoacid generator, an acid diffusion control agent, and a solvent). It is assumed that the step (1-2) is completed when at least one of the resin, the photoacid generator, the acid diffusion control agent, and the solvent is started to be added. However, in this case, while the step (2) is being performed, the mixing of the contents in the container may be continued following the step (1-2).
The addition of at least one of the resin, the photoacid generator, the acid diffusion control agent, and the solvent in step (2) is added to the container contained in the container used in step (1). It may be carried out, or it may be carried out for the contents transferred to another container or the like.
In step (2), when at least one of the resin, the photoacid generator, the acid diffusion control agent, and the solvent is added, the contents may or may not be agitated. It is good, but it is preferable that the resin composition is agitated from the viewpoint of improving the uniformity of the obtained sensitive light-sensitive or radiation-sensitive resin composition.
In the production method of the present invention, the inside of the container may be continuously stirred from the start of the step (1) to the end of the step (2). Further, the inside of the container may be stirred even after the completion of the step (2) (after the addition of at least one of the resin, the photoacid generator, the acid diffusion control agent, and the solvent) is completed.

The amount of material to be added in step (2) (total amount if there are multiple types of materials to be added) is the total amount of resin, photoacid generator, acid diffusion control agent, and solvent put in the container in step (1). 0.001 to 100% by mass is preferable, 0.001 to 50% by mass is more preferable, and 0.001 to 30% by mass is further preferable.

As one of the preferred embodiments of the present invention, after step (1), the container (composition containing resin, photoacid generator, acid diffusion control agent, and solvent) is divided into two or more fractions. Then, there is an embodiment in which the physical properties are evaluated using at least one of the above fractions. In this case, it is preferable to perform step (2) on a fraction different from the fraction used in the above evaluation. In this embodiment, the “container in the container is divided into two or more fractions, and at least one of the above fractions is used to evaluate the physical properties, which is performed between the steps (1) and (2). The "step to be performed" is also referred to as a step (B).

The evaluation in the step (B) is not particularly limited, but for example, an evaluation of the physical characteristics of the film performed on an organic film formed by using at least one of the above fractions, or at least one of the above fractions. For example, the evaluation of the physical characteristics of the solution is performed.

That is, as one of the preferred embodiments of the present invention, an organic film is formed using at least one of the above fractions, the physical characteristics of the organic film are evaluated, and the target film is based on the result of the evaluation. An embodiment in which the above step (2) is performed in order to adjust the physical properties can be mentioned. The film physical characteristics are preferably at least one of sensitivity, film thickness, contact angle (for example, contact angle of water), complex refractive index, transmittance, and refractive index.
In order to adjust the sensitivity, it is conceivable to add, for example, an acid diffusion control agent.
In order to adjust the film thickness, for example, it is conceivable to add a solvent.
In order to adjust the contact angle, for example, it is conceivable to add a resin.
In order to adjust the complex refractive index, for example, it is conceivable to add a photoacid generator.
In order to adjust the transmittance, it is conceivable to add, for example, a photoacid generator.
In order to adjust the refractive index, for example, it is conceivable to add a resin.

Further, as one of the preferred embodiments of the present invention, the solution physical characteristics are evaluated using at least one of the above fractions, and based on the result of the evaluation, the above step (2) is performed in order to adjust the solution physical characteristics to the desired one. ). The physical characteristics of the solution are preferably at least one of a complex refractive index, a transmittance, and a refractive index.
In order to adjust the complex refractive index, for example, it is conceivable to add a photoacid generator.
In order to adjust the transmittance, it is conceivable to add, for example, a photoacid generator.
In order to adjust the refractive index, for example, it is conceivable to add a resin.

<Other processes>
The production method of the present invention may have other steps in addition to the above-mentioned steps (1), steps (1-2), steps (B) and steps (2).
For example, after the step (2), there may be a step (3) of further mixing the contents in the container. Further, it may have a step of performing filtration (for example, filter filtration) at any timing before the step (1) is performed or after the step (1) is performed.

[Pattern formation method]
The actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention described above can be used for pattern formation in, for example, a manufacturing process of a semiconductor device.
The sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is typically a resist composition (preferably a chemically amplified resist composition), and is a positive resist composition. It may be a negative resist composition. Further, the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention may be a resist composition for alkaline development or a resist composition for organic solvent development.

The pattern forming method using the actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is not particularly limited, but it is preferable to have the following steps.
Step a: A step of forming a resist film on a substrate using the sensitive light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention. Step b: The resist film is exposed and the exposed resist film is exposed. Step c: A step of developing an exposed resist film using a developing solution to form a pattern. Each of the above steps will be described in detail below.

(Step a: Resist film forming step)
Step a is a step of forming a resist film on a substrate using the actinic cheilitis or radiation-sensitive resin composition produced by the production method of the present invention.

Examples of the method of forming a resist film on a substrate using the actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention include a method of applying the above composition on the substrate.
It is preferable to filter the composition as necessary before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

The actinic light-sensitive or radiation-sensitive resin composition produced by the production method of the present invention has a spinner, a coater, or the like on a substrate (eg, silicon, silicon dioxide coating) such as that used in the production of integrated circuit elements. It can be applied by an appropriate application method of. As a coating method, spin coating using a spinner is preferable.
After applying the above composition, the substrate may be dried to form a resist film. If necessary, various undercoat films (inorganic film, organic film, or antireflection film) may be formed under the resist film.

Examples of the drying method include a heating method (pre-baking: PB). The heating can be performed by a means provided in a normal exposure machine and / or a developing machine, and may be performed by using a hot plate or the like.
The heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C.
The heating time is preferably 30 to 1000 seconds, more preferably 40 to 800 seconds.

The film thickness of the resist film is not particularly limited, but in the case of a resist film for KrF exposure, 0.2 to 12 μm is preferable, and 0.3 to 5 μm is more preferable.
Further, in the case of a resist film for ArF exposure or EUV exposure, 30 to 700 nm is preferable, and 40 to 400 nm is more preferable.

A top coat may be formed on the upper layer of the resist film by using the top coat composition.
It is preferable that the topcoat composition is not mixed with the resist film and can be uniformly applied to the upper layer of the resist film.
The film thickness of the top coat is preferably 10 to 200 nm, more preferably 20 to 100 nm.
The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs 0072 to 0082 of JP-A-2014-059543.

(Step b: Exposure step)
Step b is a step of exposing the resist film to obtain the exposed resist film.
Examples of the exposure method include a method of irradiating the formed resist film with active light rays or radiation through a predetermined mask.
Examples of the active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, and EB (Electron Beam), preferably 250 nm or less, more preferably 220 nm or less. more preferably far ultraviolet light at a wavelength of 1 ~ 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), _{F 2} excimer laser (157nm), EUV (13nm) , X -ray, and, EB can be mentioned.

It is preferable to bake (post-exposure bake: PEB) after exposure and before developing.
The heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C.
The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds.
The heating can be performed by a means provided in a normal exposure machine and / or a developing machine, and may be performed by using a hot plate or the like.
This step is also referred to as post-exposure baking.

(Step c: Development step)
Step c is a step of developing the exposed resist film using a developing solution to form a pattern.

As a developing method, a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), and a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle method). , A method of spraying the developer on the surface of the substrate (spray method), and a method of continuing to eject the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic discharge method). Can be mentioned.
Further, after the step of performing the development, a step of stopping the development may be carried out while substituting with another solvent.
The developing time is not particularly limited as long as the resin in the unexposed portion is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
The temperature of the developing solution is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.

Examples of the developing solution include an alkaline developing solution and an organic solvent developing solution.
As the alkaline developer, it is preferable to use an alkaline aqueous solution containing an alkali. Above all, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH). An appropriate amount of alcohols, surfactants and the like may be added to the alkaline developer. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10.0 to 15.0.

The organic solvent developer is a developer containing an organic solvent.
Examples of the organic solvent used in the organic solvent developing solution include known organic solvents, and examples thereof include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

(Other processes)
The pattern forming method preferably includes a step of washing with a rinsing liquid after the step c.
Examples of the rinsing solution used in the rinsing step after the step of developing with an alkaline developer include pure water. An appropriate amount of surfactant may be added to the rinse solution.

The rinse solution used in the rinse step after the development step using the organic developer is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. As the rinsing solution, a rinsing solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent is used. Is preferable. An appropriate amount of surfactant may be added to the rinse solution.

Further, the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in the step c may be used as a mask to process the substrate (or the underlayer film and the substrate) to form the pattern on the substrate.
The processing method of the substrate (or the underlayer film and the substrate) is not particularly limited, but the substrate (or the underlayer film and the substrate) is dry-etched using the pattern formed in step c as a mask to obtain the substrate. The method of forming the pattern is preferable.
The dry etching may be one-step etching or multi-step etching. When the etching is an etching consisting of a plurality of stages, the etching of each stage may be the same process or different processes.
Any known method can be used for etching, and various conditions and the like are appropriately determined according to the type and application of the substrate. For example, the Bulletin of the International Society of Optical Engineering (Proc. Of SPIE) Vol. Etching can be performed according to 6924, 692420 (2008), Japanese Patent Application Laid-Open No. 2009-267112, and the like. It is also possible to follow the method described in "Chapter 4 Etching" of "Semiconductor Process Textbook 4th Edition 2007 Published Publisher: SEMI Japan".
Of these, oxygen plasma etching is preferable as the dry etching.

It is preferable that the various materials used in the present invention (for example, solvent, developer, rinsing liquid, antireflection film forming composition, top coat forming composition, etc.) do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppt (parts per million) or less, and further preferably 100 mass ppt (parts per million) or less. 10 mass ppt or less is particularly preferable, and 1 mass ppt or less is most preferable. Here, as metal impurities, Na, K, Ca, Fe, Cu, Mn, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Mo, Zr, Pb, Examples thereof include Ti, V, W, and Zn.

Examples of the method for removing impurities such as metals from the various materials include filtration using a filter. The filter pore diameter is preferably 0.20 μm or less, more preferably 0.05 μm or less, and even more preferably 0.01 μm or less.
As the material of the filter, fluororesins such as polytetrafluoroethylene (PTFE) and perfluoroalkoxy alkane (PFA), polyolefin resins such as polypropylene and polyethylene, and polyamide resins such as nylon 6 and nylon 66 are preferable. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of or a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination. Further, various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step. As the circulation filtration step, for example, a method disclosed in JP-A-2002-62667 is preferable.
The filter preferably has a reduced amount of eluate as disclosed in Japanese Patent Application Laid-Open No. 2016-201426.
In addition to filter filtration, impurities may be removed by an adsorbent, and filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in JP-A-2016-206500.
Further, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. Alternatively, a method such as lining or coating the inside of the apparatus with a fluororesin or the like to perform distillation under conditions in which contamination is suppressed as much as possible can be mentioned. The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as the above-mentioned conditions.
The above-mentioned various materials are stored in the containers described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Laid-Open No. 2015-123351, Japanese Patent Application Laid-Open No. 2017-13804, etc. in order to prevent contamination with impurities. It is preferable to be done.
Various materials may be diluted with the solvent used in the composition and used.

The present invention also relates to a method for manufacturing an electronic device including the above-mentioned pattern forming method, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is suitably mounted on an electrical and electronic device (home appliance, OA (Office Automation), media-related device, optical device, communication device, etc.).

Hereinafter, the present invention will be described in more detail based on Examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not construed as limiting by the examples shown below.

<Resin>
The following resins were used in Examples and Comparative Examples. All of the following resins were synthesized based on known techniques.
Polymer-A to Polymer-E and Polymer-G to Polymer-J are resins (A), and Polymer-F is an alkali-soluble resin.
The weight average molecular weight (Mw) and the dispersity (Mw / Mn) of the resin are polystyrene-equivalent values measured by the above-mentioned GPC method (carrier: tetrahydrofuran (THF)). The composition ratio (mol% ratio) of the repeating unit in the resin ^{was measured by 13} C-NMR (nuclear magnetic resonance).

<Photoacid generator (C)>
The structures of the compounds used as photoacid generators in Examples and Comparative Examples are shown below.

<Acid diffusion control agent (D)>
The structure of the compound used as the acid diffusion control agent in Examples and Comparative Examples is shown below.

<Surfactant (E)>
A resin, Polymer-X or Polymer-Y, was used as the surfactant.

Polymer-Y: Mega Fvck R-41 (manufactured by DIC Corporation)

<Hydrophobic resin (F)>
The structure of Polymer-Z used as the hydrophobic resin (F) is shown below. As Polymer-Z, one synthesized based on a known technique was used.
The weight average molecular weight (Mw) of Polymer-Z is a polystyrene-equivalent value measured by the above-mentioned GPC method (carrier: tetrahydrofuran (THF)). The composition ratio (mol% ratio) of the repeating unit in the resin ^{was measured by 13} C-NMR (nuclear magnetic resonance).

<Solvent (S)>
The solvents used in Examples and Comparative Examples are shown below.
PGMEA: Propylene Glycol Monomethyl Ether Acetate PGME: Propylene Glycol Monomethyl Ether EL: Ethyl Lactate CyHx: Cyclohexanone GBL: γ-Butyrolactone

(Example 1 KrF exposure, positive development)
<Manufacture of Actinic Cheilitis or Radiation Sensitive Resin Composition>
A resist composition was produced as follows using a production apparatus as shown in FIG. 1 as an apparatus for producing the resist composition.

Step (1): The resin, photoacid generator (C), acid diffusion control agent (D), solvent (S) and added polymer shown in Table 1 were placed in a stirring tank (volume 100 L). The input amount of each component excluding the solvent (S) in the step (1) was adjusted so that the ratio (mass%) of all the components excluding the solvent (S) to the total was as shown in Table 1. As for the amount of the solvent (S) to be added, Table 1 shows the solid content concentration (mass%) of the actinic cheilitis or radiation-sensitive resin composition (resist composition 1) obtained through the step (2) described later. Adjusted to the value shown.

Step (1-2): The contents in the stirring tank were stirred with a stirring blade at 23 ° C. and 150 rpm for 2 hours.

Step (B): 0.1 kg was separated from the contents after the step (1-2). The physical properties shown below were evaluated using the 0.1 kg fraction collected. The results of the evaluation of the physical properties shown below are not described in this specification.
-Evaluation of film physical characteristics-
A 0.1 kg fraction fractionated at a constant rotation speed by a spin coating method was spin coated on a Si substrate and baked at a temperature of 80 to 150 ° C. for 45 to 120 seconds to form an organic film (for example,). In Example 1, baking was performed at 130 ° C. for 90 seconds).
The Si substrate may be treated with hexamethyldisilazane, or may be treated with BARC (Bottom Anti Reflection Coat) in order to suppress reflection.
The sensitivity, film thickness, contact angle, complex refractive index, transmittance, and refractive index of the obtained organic film were evaluated as follows.

-A pattern for sensitivity evaluation was formed on the sensitivity organic film, and CD (critical dimension) measurement was performed using a scanning electron microscope (SEM) (S-9380II; manufactured by Hitachi, Ltd.). Sensitivity represents the dose amount (exposure amount) at the target CD value.
The method for forming the sensitivity evaluation pattern is as follows.
The wafer on which the organic film was formed was subjected to pattern exposure through an exposure mask using a KrF excimer laser scanner (ASML, PAS5500 / 850C, wavelength 248 nm, NA 0.50) (for example, in Example 1, a line was formed. A width of 150 nm, a 1: 1 line and space pattern was formed). Then, it was baked at a temperature of 80 to 140 ° C. for 45 to 120 seconds (Post Exposure Bake; PEB) (for example, in Example 1, it was baked at 130 ° C. for 60 seconds). Then, it was developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) (hereinafter, also referred to as “TMAHaq”) as a developing solution for 30 to 60 seconds, and spin-dried. In this way, a sensitivity evaluation pattern was obtained.

-Film thickness The organic film was measured at multiple points with a film thickness meter (VM-3210; manufactured by SCREEN), and the average value was taken as the film thickness.

-Contact angle The contact angle of pure water of the organic membrane was measured with a contact angle meter (DM-700; manufactured by Kyowa Interface Science Co., Ltd.) and used as the contact angle.

-Complex refractive index, transmittance, refractive index The organic film was measured (1.2 to 7.0 eV) by an ellipsometer (M-2000D; manufactured by JA Woollam Japan), and the complex refractive index, refractive index, and transmittance were measured. I got a rate.

-Evaluation of solution physical characteristics-
The complex refractive index, transmittance, and refractive index of the 0.1 kg fraction collected were measured (200 to 400 nm) using an absorptiometer (manufactured by Shimadzu Corporation).

Step (2): Additional material 1 (Polymer-X) shown in Table 2 was added to the contents in the stirring tank. The amount of the additional material 1 (Polymer-X) added in the step (2) is the total amount of the resin, the photoacid generator, the acid diffusion control agent, and the solvent added in the step (1) (in Table 2, "Step (1)". The amount (mass%) of the additional material 1 (Polymer-X) added to the total amount (%) in ()) was adjusted to be the value shown in Table 2.
From the start of the step (1) to the end of the step (2), the inside of the container was continuously stirred by the stirring blade.
In addition, after the completion of step (2) (after adding all the additional materials), the contents were continuously stirred for 4 hours.
Next, the contained material (solution) obtained in the step (2) is filtered by a nylon film having a pore size of 0.01 to 0.15 μm, or a polyolefin resin or fluorine having a pore size of 0.003 to 0.10 μm. A filter provided with a resin film was passed through to produce a sensitive light-sensitive or radiation-sensitive resin composition (resist composition 1). The filter filtration can also be performed under a pressurizing condition of 0.12 MPa using, for example, a filter having a pore size of 0.1 μm made of a nylon film and a filter having a pore size of 0.03 μm made of polyethylene. A plurality of filters may be arranged in series or may be circulated.
The solid content concentration of the actinic cheilitis or radiation-sensitive resin composition (resist composition 1) was the value shown in Table 1 (8.4% by mass).

<Evaluation of agglutination defects caused by materials>
[Pattern formation KrF exposure, positive development]
The resist composition prepared above has a target film thickness (for example, 700 nm in Example 1) without providing an antireflection layer on a Si substrate (manufactured by Advanced Materials Technology) treated with hexamethyldisilazane. Spin-coat at a rotation speed (for example, 1500 rpm in Example 1), bake (PreBake; PB) at a temperature of 80 to 150 ° C. for 45 to 120 seconds, and apply an anti-reflective or radiation-sensitive film (resist film). Formed. The wafer on which the resist film was formed was subjected to pattern exposure through an exposure mask using a KrF excimer laser scanner (ASML, PAS5500 / 850C, wavelength 248 nm, NA 0.50) (for example, in Example 1, a line was formed. A width of 150 nm, a 1: 1 line and space pattern was formed). Then, it was baked at a temperature of 80 to 140 ° C. for 45 to 120 seconds (Post Exposure Bake; PEB) (for example, in Example 1, it was baked at 130 ° C. for 60 seconds). Then, it was developed with TMAHaq for 30 to 60 seconds and spin-dried. In this way, a defect evaluation pattern was obtained.

[evaluation]
A pattern was formed as described above, and defect evaluation was performed using a defect evaluation device (KLA2360; manufactured by KLA-Tencor). A review image was acquired by a review SEM (SEMVision G3E FIB; manufactured by AMAT), and the number of agglutination defects caused by the material was counted.
The results are shown in Table 2 below.

In Tables 1 and 2 below, the "%" described as the unit of the input amount of each material, the addition amount of the additional materials (additional materials 1 to 4), and the solid content concentration of the resist composition are all based on mass (that is,). "Mass%"). The unit "h" of stirring time represents "time". The ratio of the solvent used is the mass ratio of various solvents to the total solvent. The same applies to Tables 3 to 5 below.

(Examples 2 to 19 KrF exposure, positive development)
The table shows the types and amounts of each component used, the stirring time in step (1-2), the types and amounts of additional materials added, and the solid content concentration of the obtained actinic or radiation-sensitive resin composition. Actinic light-sensitive or radiation-sensitive resin compositions (resist compositions 2 to 19) were obtained in the same manner as in Example 1 except that the contents were changed to those shown in 1 and Table 2. Further, a pattern was formed in the same manner as in Example 1, and agglutination defects caused by the material were evaluated.

(Example 20 KrF exposure, negative development)
The table shows the types and amounts of each component used, the stirring time in step (1-2), the types and amounts of additional materials added, and the solid content concentration of the obtained actinic or radiation-sensitive resin composition. An actinic light-sensitive or radiation-sensitive resin composition (resist composition 20) was obtained in the same manner as in Example 1 except that the contents were changed to those shown in 1 and Table 2.
An exposure mask in which the light transmitting portion and the light-shielding portion of the exposure mask used in Example 1 (positive development) were inverted was used, n-butyl acetate (nBA) was used as a developing solution, and methylisobutylcarbinol was used as a rinsing solution. A pattern was formed in the same manner as in Example 1 except that the above was used, and the aggregation defects caused by the material were evaluated.

(Examples 21 to 28 ArF exposure, positive development)
The table shows the types and amounts of each component used, the stirring time in step (1-2), the types and amounts of additional materials added, and the solid content concentration of the obtained actinic or radiation-sensitive resin composition. Actinic light-sensitive or radiation-sensitive resin compositions (resist compositions 21 to 28) were obtained in the same manner as in Example 1 except that the contents were changed to those shown in 3 and Table 4.
Further, the pattern is the same as in Example 1 except that an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA0.85, Anal, outer sigma 0.9, inner sigma 0.6) is used as the exposure light source. Was formed, and the aggregation defects caused by the material were evaluated. Ultrapure water was used as the immersion liquid.

(Example 29 ArF exposure, negative development)
The table shows the types and amounts of each component used, the stirring time in step (1-2), the types and amounts of additional materials added, and the solid content concentration of the obtained actinic or radiation-sensitive resin composition. A sensitive light-sensitive or radiation-sensitive resin composition (resist composition 29) was obtained in the same manner as in Example 1 except that the contents were changed to those shown in 3 and Table 4.
An exposure mask in which the light transmitting portion and the light-shielding portion of the exposure mask used in Example 21 (positive development) were inverted was used, n-butyl acetate (nBA) was used as a developing solution, and methylisobutylcarbinol was used as a rinsing solution. A pattern was formed in the same manner as in Example 21 except that the above was used, and the aggregation defects caused by the material were evaluated.

(Example 30 ArF exposure, negative development)
The table shows the types and amounts of each component used, the stirring time in step (1-2), the types and amounts of additional materials added, and the solid content concentration of the obtained actinic or radiation-sensitive resin composition. A sensitive light-sensitive or radiation-sensitive resin composition (resist composition 30) was obtained in the same manner as in Example 1 except that the contents were changed to those shown in 3 and Table 4.
A pattern was formed in the same manner as in Example 29 except that 2-heptanone (MAK) was used as the developing solution, and agglutination defects caused by the material were evaluated.

(Example 31 i-line exposure, positive development)
The table shows the types and amounts of each component used, the stirring time in step (1-2), the types and amounts of additional materials added, and the solid content concentration of the obtained actinic or radiation-sensitive resin composition. A sensitive light-sensitive or radiation-sensitive resin composition (resist composition 31) was obtained in the same manner as in Example 1 except that the contents were changed to those shown in 3 and Table 4.
Further, a pattern was formed in the same manner as in Example 1 except that an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) was used as an exposure light source, and agglutination defects caused by the material were evaluated. rice field.

(Examples 32 to 34 EUV exposure, positive development)
The table shows the types and amounts of each component used, the stirring time in step (1-2), the types and amounts of additional materials added, and the solid content concentration of the obtained actinic or radiation-sensitive resin composition. Actinic light-sensitive or radiation-sensitive resin compositions (resist compositions 32 to 34) were obtained in the same manner as in Example 1 except that the contents were changed to those shown in 3 and Table 4.
Further, the pattern was formed in the same manner as in Example 1 except that an EUV exposure device (Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech) was used as the exposure light source. It was formed and the aggregation defects caused by the material were evaluated.

(Example 35 EUV exposure, negative development)
The table shows the types and amounts of each component used, the stirring time in step (1-2), the types and amounts of additional materials added, and the solid content concentration of the obtained actinic or radiation-sensitive resin composition. A sensitive light-sensitive or radiation-sensitive resin composition (resist composition 35) was obtained in the same manner as in Example 1 except that the contents were changed to those shown in 3 and Table 4.
An exposure mask in which the light transmitting portion and the light-shielding portion of the exposure mask used in Example 32 (positive development) were inverted was used, n-butyl acetate (nBA) was used as a developing solution, and methylisobutylcarbinol was used as a rinsing solution. A pattern was formed in the same manner as in Example 32 except that the above was used, and the aggregation defects caused by the material were evaluated.

(Example 36 to Example 37 Electron beam exposure, positive development)
The table shows the types and amounts of each component used, the stirring time in step (1-2), the types and amounts of additional materials added, and the solid content concentration of the obtained actinic or radiation-sensitive resin composition. Actinic light-sensitive or radiation-sensitive resin compositions (resist compositions 36 to 37) were obtained in the same manner as in Example 1 except that the contents were changed to those shown in 3 and Table 4.
Further, a pattern was formed in the same manner as in Example 1 except that an electron beam drawing apparatus (manufactured by Elionix Inc.; ELS-7500, acceleration voltage 50 keV) was used as the exposure light source, and agglutination defects caused by the material were formed. Evaluation was performed.

(Comparative Examples 1 to 3, 10, 11 KrF exposure, positive development)
The type and amount of each component used, the stirring time in step (1-2), and the solid content concentration of the obtained actinic cheilitis or radiation-sensitive resin composition were changed to the contents shown in Table 5. Actinic light-sensitive or radiation-sensitive resin compositions (resist compositions r1 to r3, r10, r11) were obtained in the same manner as in Example 1 except that no additional material was added. Further, a pattern was formed in the same manner as in Example 1, and agglutination defects caused by the material were evaluated.

(Comparative Example 4 KrF exposure, negative development)
The type and amount of each component used, the stirring time in step (1-2), and the solid content concentration of the obtained actinic cheilitis or radiation-sensitive resin composition were changed to the contents shown in Table 5. An actinic light-sensitive or radiation-sensitive resin composition (resist composition r4) was obtained in the same manner as in Example 1 except that no additional material was added.
An exposure mask in which the light transmitting portion and the light-shielding portion of the exposure mask used in Example 1 (positive development) were inverted was used, n-butyl acetate (nBA) was used as a developing solution, and methylisobutylcarbinol was used as a rinsing solution. A pattern was formed in the same manner as in Example 1 except that the above was used, and the aggregation defects caused by the material were evaluated.

(Comparative Examples 5 to 6 ArF exposure, positive development)
The type and amount of each component used, the stirring time in step (1-2), and the solid content concentration of the obtained actinic cheilitis or radiation-sensitive resin composition were changed to the contents shown in Table 5. Actinic light-sensitive or radiation-sensitive resin compositions (resist compositions r5 to r6) were obtained in the same manner as in Example 1 except that no additional material was added.
Further, the pattern is the same as in Example 1 except that an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA0.85, Anal, outer sigma 0.9, inner sigma 0.6) is used as the exposure light source. Was formed, and the aggregation defects caused by the material were evaluated. Ultrapure water was used as the immersion liquid.

(Comparative Example 7 i-line exposure, positive development)
The type and amount of each component used, the stirring time in step (1-2), and the solid content concentration of the obtained actinic cheilitis or radiation-sensitive resin composition were changed to the contents shown in Table 5. An actinic light-sensitive or radiation-sensitive resin composition (resist composition r7) was obtained in the same manner as in Example 1 except that no additional material was added.
Further, a pattern was formed in the same manner as in Example 1 except that an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) was used as an exposure light source, and agglutination defects caused by the material were evaluated. rice field.

(Comparative Example 8 EUV exposure, positive development)
The type and amount of each component used, the stirring time in step (1-2), and the solid content concentration of the obtained actinic cheilitis or radiation-sensitive resin composition were changed to the contents shown in Table 5. An actinic light-sensitive or radiation-sensitive resin composition (resist composition r8) was obtained in the same manner as in Example 1 except that no additional material was added.
Further, the pattern was formed in the same manner as in Example 1 except that an EUV exposure device (Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech) was used as the exposure light source. It was formed and the aggregation defects caused by the material were evaluated.

(Comparative Example 9 Electron beam exposure, positive development)
The type and amount of each component used, the stirring time in step (1-2), and the solid content concentration of the obtained actinic cheilitis or radiation-sensitive resin composition were changed to the contents shown in Table 5. An actinic light-sensitive or radiation-sensitive resin composition (resist composition r9) was obtained in the same manner as in Example 1 except that no additional material was added.
Further, a pattern was formed in the same manner as in Example 1 except that an electron beam drawing apparatus (manufactured by Elionix Inc.; ELS-7500, acceleration voltage 50 keV) was used as the exposure light source, and agglutination defects caused by the material were formed. Evaluation was performed.

Compared with the resist compositions produced by Comparative Examples 1 to 11 which are production methods without adding additional materials, the resist compositions of Examples produced by using the production method of the present invention have agglomeration defects due to the materials. It was improved.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on February 27, 2020 (Japanese Patent Application No. 2020-032275), the contents of which are incorporated herein by reference.

10 Stirring tank 12 Stirring shaft 14 Stirring blade 16 Circulation piping 18 Filter 20 Discharge piping 22 Discharge nozzle 100 Manufacturing equipment

Claims

The step (1) of putting a resin, a compound that generates an acid by irradiation with active light or radiation, an acid diffusion control agent, and a solvent into a container, and
The resin, the compound that generates an acid by irradiation with the active light or radiation, the acid diffusion control agent, and the compound that generates acid by irradiation with the active light or radiation in a container containing the solvent. A method for producing a sensitive light-sensitive or radiation-sensitive resin composition, which comprises the step (2) of adding at least one of the acid diffusion control agent and the solvent in this order.
The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to claim 1, wherein the step (2) is performed 30 minutes or more after the step (1) is completed.
Between the step (1) and the step (2)
The actinic cheilitis according to claim 1 or 2, further comprising a step (1-2) of mixing the resin, the compound that generates an acid by irradiation with the active light or radiation, the acid diffusion control agent, and the solvent. Alternatively, a method for producing a radiation-sensitive resin composition.
The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to claim 3, wherein the mixing time in the step (1-2) is 2 hours or more.
The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to claim 3 or 4, wherein the mixing time in the step (1-2) is 4 hours or more.
The method for producing a sensitive actinic or radiation-sensitive resin composition according to any one of claims 3 to 5, wherein the mixing time in the step (1-2) is 8 hours or more.
The production of the sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein the solid content concentration of the sensitive light-sensitive or radiation-sensitive resin composition is 10% by mass or more. Method.
The compound that generates an acid by irradiation with active light or radiation is at least one selected from the compound represented by the following general formula (ZI-3) and the compound represented by the following general formula (ZI-4). The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7.

In the general formula (ZI-3),
R 1c to R 5c are independently hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group. , Nitro group, alkylthio group or arylthio group.
R 6c and R 7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.
Any two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y are each combined to form a ring structure. The ring structure may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Zc - represents an anion.

In the general formula (ZI-4),
l represents an integer of 0 to 2.
r represents an integer from 0 to 8.
R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxycarbonyl group.
R 14 represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a cycloalkylsulfonyl group. When a plurality of R 14s exist, they may be the same or different.
Each of R 15 independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Bonded to two R 15 each other may form a ring. When two R 15 are combined to form a ring together, it may contain a hetero atom in the ring skeleton.
Z - represents an anion.
After the step (1)
The actinic cheilitis according to any one of claims 1 to 8, wherein the contained substance in the container is divided into two or more fractions, and the physical properties are evaluated using at least one of the fractions. Alternatively, a method for producing a radiation-sensitive resin composition.
An organic film is formed using at least one of the fractions, the film physical characteristics of the organic film are evaluated, and based on the evaluation result, the step (2) is performed in order to adjust to the desired film physical properties. The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to claim 9.
The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to claim 10, wherein the film physical characteristics are at least one of sensitivity, film thickness, contact angle, complex refractive index, transmittance, and refractive index. ..
The sensitivity according to claim 9, wherein at least one of the fractions is used to evaluate the physical characteristics of the solution, and based on the result of the evaluation, the step (2) is performed in order to adjust to the desired physical characteristics of the solution. A method for producing a light-emitting or radiation-sensitive resin composition.
The method for producing a sensitive light-sensitive or radiation-sensitive resin composition according to claim 12, wherein the solution physical characteristics are at least one of a complex refractive index, a transmittance, and a refractive index.
A step of forming a resist film on a substrate using a sensitive light-sensitive or radiation-sensitive resin composition produced by the production method according to any one of claims 1 to 13.
A step of exposing the resist film to obtain an exposed resist film, and
A step of developing the exposed resist film using a developing solution to form a pattern, and
A pattern forming method.
A method for manufacturing an electronic device, including the pattern forming method according to claim 14.